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By W. D. Potter, E. T. Peters

Single-crystal films of boron have been prepared by thermal reduction of purified BCl3 with subsequent deposition of boron onto oriented silicon substrates. The structural properties of films prepared under various experimental conditions have been determined by light microscopy and "grazing-" angle electron-diffraction analysis. An orientation relationship is proposed for silicon and a-rhombo-heclral boron which can be described as: (111)Si (112)B; [110]Si [110]B ElEMENTAL boron is known to have a high energy gap* and consequently has potential value as a high- *Energy gaps of 1.35 to 1.55 ev1-3 and 2.0 ev4 are reported for ß-rhombohedra1 and a-rhombohedra1 boron, respectively. temperature semiconductor.5 Exploitation of this property, however, has been hampered by the unavailability of pure, single-crystal boron. Two recent symposia6,7 have treated the subjects of purification, crystallization, crystal structure, and properties of boron and provide a foundation for further investigation in these areas. The structure, lattice constants, and observed ranges of stability for four reported polymorphs of boron8°12 are listed in Table I. The rhombohedral structures are generally accepted as true polymorphs whereas the tetragonal structures are believed to be transient. Most currently available single crystals of boron are grown by Czochralski and floating-zone methods. Unfortunately, these crystals generally contain numerous defects and are highly strained as a result of the polymorphic transformations and thermal contractions which accompany cooling. Recently, Armington, Potter, and Tanner13 have reported the formation of single-crystal films of boron on silicon single-crystal substrates through thermal reduction of BC13 by hydrogen. Boron E. T. PETERS, Junior Member AIME, is Senior Scientist, ManLabs, Inc., Cambridge, Mass., and W. D. POTTER is Research Chemist, Air Force Cambridge Research Loboratories, L. G. Hanscom Field, Bedford, Mass. formed at temperatures near 1000°C was identified as the a-rhombohedra1 form, consistent with expectation. The present paper describes a continuation of this work with specific reference to characterization of the structural features of the deposited boron films. The ultimate goal of this program is to produce large-area single-crystal films of a-rhombohedra1 boron to be used for electrical and optical studies by other workers. PREPARATION OF BORON FILMS The experimental procedure of preparing thin films is similar to that described by Theuerer14 for the epitaxial growth of silicon by thermal reduction of SiC14 and has already been described as applied to the preparation of boron thin films.13 Briefly, a mixture of BCl3 vapor and dry hydrogen is passed over a heated silicon substrate. Thermal reduction of the BC13 allows deposition of boron on the substrate. The substrates were {111}-oriented, single-crystal silicon. Square specimens 0.63 cm on an edge by 0.1 to 3.0 mm thickness were prepared by

Jan 1, 1965

By W. S. Pellini, F. N. Rhines

IN many of the otherwise well established alloy phase diagrams the solidus curves (temperatures at which liquid first appears upon melting) have not been located accurately, chiefly because the experimental techniques that have been most popular for determining solidus temperatures have been both cumbersome and subject to large errors. C. E. Homer and H. Plummer1 have described a sensitive and at the same time a very simple technique for locating the solidus curves in a number of alloys of tin. Their method consists simply in noting the temperature at which a specimen of the alloy ruptures under the influence of a light bending force. Although this method is not new, it has been little used for this purpose in the past; nevertheless, it appears so attractive in its possibilities of speed, simplicity, and precision that the investigations presently to be described were undertaken to verify its merits. The redetermination of the solidus and eutectic temperatures of the lead-antimony system was employed as a medium 0f experimentation. New values obtained in this way are believed to be sufficiently precise to warrant a revision of the currently accepted lead-antimony phase diagram (Fig. I). Determinations of the solidus of the lead-rich lead-antimony alloy series have been published by R. S. Dean2 and by E. E. Schumacher and F. C. Nix.3 Their points are represented in Fig. I. In their work the solidus was not located at antimony concentrations greater than 2 per cent; the curve was presumed to meet the eutectic horizontal at an antimony concentration of about 2.5 per cent. In the present studies the solidus has been traced to 3.5 per cent, where the eutectic horizontal is intersected (Table I and Fig. I). Within the range investigated by Dean and by Schumacher and Nix the agreement with their values is good. H. Seltz and B. De Witt,4 on the basis of activity measurements, have calculated that the intersection of the solidus and the eutectic reaction horizontal should lie at 3.86 per cent of antimony. The following determinations of the eutectic temperature have been reported: Roland-Gosselin,5 228°C.; Ewen,6 228°C.; J. E. Stead,7 247°C.; Campbell,8 228°C.; W. Gontermann,9 245° to 252°C.; R. Loebe,10 245°C.; E. Heyn and 0. Bauer,11 245°C.; H. Endo,12 250°C.; R. S. Dean,2 249° to 258°C.; E. Abel, 0. Redlich, and J. Adler,13 245°C.; W. Broniewski and L. Sliwowski,14 250° to 252°C.; H. Seltz and B. De Witt,4 250°C. A temperature of 249°C- appears to have been generally accepted in recent years; it is the value most frequently obtained by the method of cooling curves. Values below 249°C. have usually been obtained by inferior cooling-curve techniques; those above 250°C., by the method of heating

Jan 1, 1942

By L. A. Shipman

The combustion of coal in fuel beds has been practiced as an art for many years; during the last 2 7 years a scientific approach to this subject has contributed a small amount of fundamental data. The subject is a very controversial one. Opinions regarding the performance of the same coal used in the same equipment in different plants may vary from "the best coal ever used in the plant" to "the worst coal ever tired." These opinions can all be true, owing to the various conditions under which the coal was used. Because of these differences, an attempt will be made in this paper to discuss coal facts and coal characteristics as related to the use phenomena observed during the art of firing coal in fuel beds for many years. The work of Kreisinger1 and his associates in the 1,'. S. Bureau of Mines, reported in 1916, was the first scientific attempt I know of to obtain factual data explaining the mechanism of combustion of fuel beds. They gave a chart showing an ignited fuel bed. The air passing up through the fuel bed first combined with the fuel by a reaction resulting in the complete combustion of carbon to CO2, which combined with the carbon in higher levels of the fuel bed to form CO with the absorption of heat. The fundamental facts produced in those experiments proved of much value and checked with practical experiences with hand-fired fuel beds. Hand firing was the prevailing method of stoking coal at that time. The order in which these reactions occur, as shown by Kreisinger and his associates, has been amply confirmed by repetition of this work with different fuels both her? and abroad. These experiments also showed that under their conditions the rate of burning was proportional to the air flow. These data were of practical value to a fireman and were accepted as generally true in all fuel beds. In later years many observations by myself in fuel beds of underfeed stokers and other thick fuel beds such as gas producers, where channeling. increase of particle size, or both, occur. indicated that, instead of the horizontal layers we had thought were present, perhaps the layers were vertical or irregular. Later investigations in fuel beds made by Mayers2 and Barnes3 indicated that the burning takes place in some instances along the surfaces of vertical or irregular channels or cracks in the fuel bed and that under these conditions a reaction occurs that differs from that in the old horizontal-layered handfired fuel beds. Examining the data in Kreisinger'sl experiments, and the information in different charts with different fuels, different retort positions and air admissions of Barnes3 and the gas analysis arid isotherms of Mayers,2 one can check experience observation and come to a conclusion that as particle size of the fuel increases with other conditions the same, the maximum CO2 and temperature

Jan 1, 1947

By C. E. Lesher

Two processes for agglomerating fine sized ores with low temperature coke are described. One process (Orcarb) agglomerates ores with limited amounts of carbon; the other (ore-carbon pellets) pelletizes fine sized ores, using low temperature cokes as the binder. Data are presented on the products obtained when taconite, magnetite, and hematite concentrates and several titanium oxide ores were used. REDUCTION of finely divided oxide ores has long been a major metallurgical problem. Various methods of agglomerating, notably briquetting, sintering, nodulizing, and pelletizing, have been developed and are in industrial use. Carbon is the usual reducing agent for oxide ores and attempts have been made to agglomerate fine ores with coking coal in order to get the metallurgical advantages of intimate contact and increased particle sizes suitable for subsequent smelting or reduction.1-3 For the past three years, research has been in progress on two processes for combining fine sized ores with reactive carbon in the form of low temperature coke. By one process, designated Orcarb, the ore is coated with coke carbon in amounts limited to that required for reduction and the result is an appreciable but limited increase in product particle size over that of the original ore. The second process, called ore-carbon pellets, produces pellets of fine ore bound by low temperature coke. The first objective was to develop a process for combining an oxide ore with only enough carbon for its reduction, the amount being that derived from the simple reduction equations. The carbon (that amount theoretically required for the reduction of the oxides in an agglomerate with ore), calculated to CO, ranges from 10 pct for zinc calcines or phosphate ores to 21 pct for rutile and 26 pct for silica. The carbon required for reducing iron oxides falls between the extremes—10 and 26 pct. When the carbon in the agglomerate is low temperature coke, reduction by hydrogen may be expected to take place, thus modifying the calculated carbon require- ment. On the other hand, in practice, an excess of reducing agent over that required in theory is normally used. Screen sizes of three iron ores on which the greater part of the experimental work was performed are given in Table I. Most of the testing was done with Freeport (Renton Mine) coal, but Pittsburgh and Elkhorn bed coals were also used. The first objective was to agglomerate the ore with sufficient low temperature coke to provide carbon for reduction, i.e., in the range from 10 to 25 pct. This was accomplished by preheating the ore, mixing with pulverized coking coal, and completing the coal carbonization in a plain steel rotating retort. The pilot retort, as it is now constituted, is shown by diagram in Fig. 1 and photograph, Fig. 2. Ore is fed into the upper kiln by a screw; it is heated to 900" to 1100°F by direct flame and it is then discharged into an insulating hopper from which it goes

Jan 1, 1956

By Albert J. Phillips

LEAD is an inexpensive metal produced and consumed in large quantities with certain chemical and physical properties that permit handling the molten metal in bulk. These properties are its low melting point, resistance to oxidation, and its negligible solvent action on iron and steel. Thus, lead is almost always melted in large iron or steel kettles, heated from beneath, and is seldom melted in either directly or indirectly fired furnaces or electric induction or arc furnaces. Even with a modest operation a kettle holding 2 or 3 tons is employed, and the size will range up to 215 tons in the large lead refineries. The methods of handling tin and its alloys are essentially the same as for lead because of the similarity in melting point and resistance to oxidation, although because of the cost of the metal the scale is more modest. In melting lead and its alloys preliminary to a casting operation it is seldom that the melting unit is completely drained of its contents. The usual procedure is to continuously charge solid metal and continuously remove small amounts of liquid metal, so that the kettle is maintained essentially full at all times. For type metals, linotype machines usually employ automatic means of adding the solid alloy to the melting pot in proportion to the removal of the liquid metal in casting slugs of type. In the casting of grids for storage batteries, frequently automatic means of charging solid metal in direct proportion to the consumption of liquid metal in the casting is used. In the manufacture of bearing alloys, new alloy is charged in direct proportion to the consumption of metal in the bearings being cast, so that at no time does the level of the metal in the melting pot lower to any great extent. Even in the manufacture of bulky commodities such as pipe, cable. sheathing, and slabs for rolled sheet, it is the practice to employ a melting kettle of several times the capacity of the casting being made. A substantial level of liquid metal in the melting kettle is thus maintained even after the casting is poured and the original metal level is quickly restored by promptly charging new metal, even though there is no immediate need to proceed with additional casting. This procedure is permissible because the amount of fuel consumed in keeping the lead molten and immediately available for use is negligibly small and the cost is more than offset by the convenience. However, this convenient procedure necessitates study and control of certain properties of lead and tin alloys that are not of serious consequence in most other alloys and for that reason are not well known. These properties are "drossing rates" and "melting segregation." DROSSING RATE Users of lead long ago observed that the rate of dross formation on the surface of the lead in their kettles or pots varied greatly from time to time. This was particularly common in places where both antimonial lead alloys and commercially pure lead were being handled.

Jan 1, 1946

By Leonard Larson

Before direct or wet smelting of copper concentrate was adopted at the McGill smelter, in November 1932, actual furnace smelting tests had indicated the possibility of smelting between 400 and 500 dry tons of wet concentrate per furnace day. Under calcine smelting practice, solid charge up to 116; tons per furnace day had been smelted. It was realized that in order to smelt wet tonnage in equivalent amount per furnace day, a higher combustion rate and higher temperatures would be necessary within the furnace. The reverberatory furnace considered in the following history of wet-smelting developments is a unit rz7 ft. long and 28 ft. 8 in. wide, inside dimensions (Fig. I). This furnace was in operation through all the years from 1934 to date. During 1933, the first complete year of direct or wet smelting, the plant was on a curtailed copper-production basis and the available concentrate tonnage to be smelted was limited. The average coal-firing rate in the reverberatory for that year was 124 tons per furnace day. This rate was lower than the average for years immediately preceding under calcine smelting practice. With this coal-firing rate, an average of 391 tons of new metal-bearing material (N.M.B.M.) was smelted per furnace day. The following year, 1934, the coal-firing rate was increased to 139 tons and the smelting rate increased to 448 tons N.M.B.M. per fur- nace day. In succeeding years production required that either more tonnage be smelted in the one furnace or an additional furnace be placed in operation. With this situation confronting the smelting department, it was determined to continue the program of increasing the coal-firing rate and also to intensify the temperature in the smelting zone of the furnace. In order to accoinplish this, various improvements were made to aid combustion within the furnace. The burners were enlarged, increased primary air was supplied to the burners, and changes were made in the furnace to enlarge and streamline the outlet, thus increasing the furnace draft. The coal-firing rate was increased yearly until 1937 when the firing rate averaged 210 tons per furnace day. Thereafter the firing rate fluctuated according to character of charge and production requirements. In general, however, with the same character of charge the smelting rate increased in almost direct proportion to the increases in firing rate. Table I shows the average coal-firing rate, smelting rate, and other pertinent data for the direct-smelting years of 1933 to 1939 inclusive, the first fivc months of 1940 and May 1940. These figures show that the water evaporated in the waste-heat boilers was in almost direct proportion to the coal-firing rate. In making comparisons in the table, it should be borne in mind that the figures, except for May 1940, are yearly averages. Because of changes in character of charge or operating conditions, records for individual days or even months

Jan 1, 1944

By E. V. Potter, E. T. Hayes, H. C. Lukens

Large volumes of hydrogen are liberated at the cathode during electrolytic precipitation of manganese. Most of the gas escapes from the electrolyte, but a considerable amount may be entrapped in the manganese plate. Gas has been observed to escape from manganese melts in puffs that bite at the surface. It has been reported that castings made with electrolytic manganese tend to rise in the molds; for this reason the manganese is often treated to remove hydrogen before the melt is made or it is premelted and used as cast manganese in making the alloys. The effect of hydrogen on the properties of manganese and its alloys is not known, but its effect on iron and iron alloys has been studied extensively.l.2 The close relationship between iron and manganese suggests that hydrogen may have a similar effect on the properties of manganese and its alloys. The purpose of this investigation was to determine the amount of hydrogen or other gases in typical commercial electrolytic manganese sheet and to investigate ways of removing it most conveniently. Apparatus The apparatus used is shown schematically in Fig. I. It consists of a chamber A in which the metal sample is placed, a vacuum or pressure gauge B, volume gauge C, vacuum pump D, hydrogen container E, auxiliary gas chamber F, and furnace G. The specimen chamber was made of two concentric quartz tubes. The outer one, a, connects with the closed gas system and is surrounded by the furnace G. A second tube, b, fits closely inside a and has a small end that projects into the space for the specimen and holds the thermocouple for measuring the temperature of the sample. The inner tube is joined to the outer tube outside the furnace, with rubber tape and sealing wax, to prevent gas leakage into or out of the closed system. This type of specimen container is loaded very easily and can be used several times if molten metal does not come in contact with the quartz. An ordinary mercury manometer B is used to measure the pressure in the system. The volume gauge C is essentially another mercury manometer, but the volume of the column is much larger than normal and the height of the mercury can be varied by raising or lowering the well H. In this apparatus the tube had a volume of IOO C.C. for a 60-cm. length. For larger changes in gas volumes, auxiliary containers F were used to increase the volume of the system by known amounts. Valves were arranged so that these auxiliary containers could be filled from the system and evacuated by the pump as often as necessary to accommodate the increases in the volume of gas in the system. The furnace G, used to heat the samples, was equipped with an automatic temperature controller, which maintained the desired temperatures within ± 5°C.

Jan 1, 1945

By P. B. Crawford, W. L. Huskey

A study has been made to determine the effects of random vertical fractures existing in a reservoir matrix on the effective matrix properties and producing characteristics of a well. The study indicated that short vertical fractures may distort the isopotentials by 1 percent in the vicinity of the fracture. A correlation was developed which showed the effect of fracture density on the producing capacity of a well. The correlation indicated that fracture shape had little effect on producing capacity, but that total fracture length was closely correlated with the producing capacity. Effective values of reservoir permeability were found to correlate closely with fracture density when measured parallel to the direction of flow. INTRODUCTION In reviewing the petroleum literature, it is found that in most analytical solutions of hydrocarbon reservoir behavior the assumption is made that the rock is uniform throughout although core analysis and well logging surveys indicate that substantially all reservoirs are heterogeneous and some are fractured. Only in recent years have investigators studied the effects of reservoir hetrogeneity. Russell1 discussed the effect of fractures in reservoirs. The literature indicates that fractures greatly affect the exploitation of man reservoirs. This is described by Elkins and Skov2 and Little-field et al. 3 Several types of reservoir heterogeneity have been studied by unsteady-state methods. In 1959, Landrum et al. 4 showed that transient phenomena in hydrocarbon reservoirs could be studied by thermal models. pickering5 studied the flow of heat in stratified linear reservoirs consisting of plates of different metals separated by sheets of rubber which were suddenly exposed to a low-temperature source at one end. Cotman6 studied both laterally and vertically heterogeneous thermal model reservoirs with special reference to cross flow. Another type of reservoir heterogeneity involves the presence of highly permeable, circular lenses around or near the wellbore which was studied by Miesch7 using a thermal and a steady-state model. Many studies have been made of the effects of induced hydraulic fractures on well performance. 8-10 Work regarding vertical fractures that exist initially in the reservoir was reported by Givens, et al.11 Since there appears to be little published work on the importance and influence on reservoir performance of fractures that exist out in the rock matrix, this study was conducted to determine the effects of vertical fractures on pressure distribution, producing capacity and the effective permeability of the reservoir rock. The analogy between the flow of electrical current through a conducting body and the flow of fluid in a porous medium provides a convenient method of studying various aspects of petroleum reservoirs. For electrical radial steady-state flow,12 For steady-state fluid flow, With the above analogy, it is only necessary to establish the ratio of the values of the electrical units in terms of the corresponding flow units to make the analogy quantitative. The ratios are shown below.

By E. V. Potter, E. T. Hayes, H. C. Lukens

LARGE volumes of hydrogen are liberated at the cathode during electrolytic precipitation of manganese. Most of the gas escapes from the electrolyte, but a considerable amount may be entrapped in the manganese plate. Gas has been observed to escape from manganese melts in puffs that ignite at the surface. It has been reported that castings made with electrolytic manganese tend to rise in the molds; for this reason the manganese is often treated to remove hydrogen before the melt is made or it is premelted and used as cast manganese in making the alloys. The effect of hydrogen on the properties of manganese and its alloys is not known, but its effect on iron and iron alloys has been studied extensively.1.2 The close relationship between iron and man¬ganese suggests that hydrogen may have a similar effect on the properties of manganese and its alloys. The purpose of this investigation was to determine the amount of hydrogen or other gases in typical commercial electrolytic manganese sheet and to investigate ways of removing it most conveniently. APPARATUS The apparatus used is shown schematically in Fig. I. It consists of a chamber A in which the metal sample is placed, a vacuum or pressure gauge B, volume gauge C, vacuum pump D, hydrogen container E, auxiliary gas chamber F, and furnace G. The specimen chamber was made of two concentric quartz tubes. The outer one, a, connects with the closed gas system and is surrounded by the furnace G. A second tube, b, fits closely inside a and has a small end that projects into the space for the specimen and holds the thermocouple for measuring the temperature of the sample. The inner tube is joined to the outer tube outside the furnace, with rubber tape and sealing wax, to prevent gas leakage into or out of the closed system. This type of specimen container is loaded very easily and can be used several times if molten metal does not come in contact with the quartz. An ordinary mercury manometer B is used to measure the pressure in the system. The volume gauge C is essentially another mercury manometer, but the volume of the column is much larger than normal and the height of the mercury can be varied by raising or lowering the well H. In this apparatus the tube had a volume of I00 c.c. for a 60-cm. length. For larger changes in gas volumes; auxiliary containers F were used to increase the volume of the system by known amounts. Valves were arranged so that these auxiliary containers could be filled from the system and evacuated by the pump as often as necessary to accommodate the increases in the volume of gas in the system. The furnace G, used to heat the samples, was equipped with an automatic temperature controller, which maintained the desired temperatures within ± 5°C.

Jan 1, 1945

By N. J. Grant, Hans Brunner

ThE materials used in this investigation were furnished by the Aluminum Co. of America and consisted of high-purity alurhinum (99.995 pct) and two aluminum-magnesium alloys containing approximately 2 and 5 pct Mg. The compositions of these alloys are listed in Table I. The materials were received as hot rolled 3/8-in. diam rods and were made from the same heats as the materials which were previously used in this laboratory.'j3 The rods were cold swaged to 1/4-in. diam by 1 in. long, and then had two parallel flats machined over the gage length 0.085 in. apart. The test bars were annealed for 10 min at 700° F, and strained 1 pct in tension at room temperature. They were electropolished (80 pct acetic acid; 20 pct perchloric acid, 70 pct concentration) at a temperature of 60°F at approximately 20 v. A grid, transverse or square, spaced 0.2 mm apart, was impressed by rolling a fine threaded screw (128 threads per in.) across the flat surfaces. The depth of the grooves was less than 5 p. For final annealing and grain size control the specimens were enclosed in aluminum foil and sealed in Vycor tubes. Annealing conditions varied from 1 hr at 700° F to 5 days at 1050° F, depending on the alloy content, to give for most of the specimens a final grain size of about 1 mm. This treatment was followed by electropol-ishing as described above. For the test series presented in Figs. 4 and 5 round specimens were used instead of flat ones, and fine machining marks served as marker lines instead of the impressed grid lines. Electropolishing was omitted. The major advantage is that the spacing of the machining marks is only about 1 u as compared to the 200 u of the impressed grid lines, permitting higher precision in strain measurements. Unfortunately the strain annealing necessary for grain size control also resulted in some preferred orientation of the grains. The preferred orientation of three arbitrary specimens was measured by X-ray diffraction methods and the averaged results are shown in Fig. 1. The possible effects of the preferred orientation on the test results will be discussed later. The testing temperatures were 410°, 515", 725", and 940° F, with one exception in the case of the 5.1 pct Mg alloy. Since the solubility limit of this alloy is 520°F, a test temperature of 545°F was cho-se sen instead of 515°F. The selection of the test temperature was based on two considerations: 1) at 900°F and above, extensive grain boundary migration made it more difficult to measure grain boundary sliding; 2) at 400°F and below, there was so little grain boundary sliding that it was again difficult to make precise measurements. The stress was chosen to give a creep rate of approximately 2.7 pct per hr in connection with Figs. 2

Jan 1, 1961

By Louis E. Toth, Alan W. Searcy

A modification of Le Claire's microscopic model for self-diffusion is developed in a form suitable for prediction of activation energies for diffusion in disordered substitutional solutions as well as in pure metals Bonding is considered as a localized interaction, and the energy of bonding between atoms of different types is taken as the arithmetic mean of the energies in the pure elements. The activation energies for vacancy formation and migration in substitutional alloys are shown to depend on the empirical constants developed for self-diffusion when the equations are adjusted for the mole fractions of the two elements. The differences in activation energies between alloys and pure metals are calculated and compared with the experimental differences. MaNY different correlations have been proposed for use in predicting activation energies for self-diffusion or diffusion in dilute alloys. Usually theories for self-diffusion cannot be applied to alloys nor can theories for dilute alloys be satisfactorily adapted to self-diffusion. We present here a correlation scheme which can approximate activation energies for diffusion, vacancy formation, and atom migration in substitutional-alloy systems of any concentration. The activation energy for self-diffusion QD has been correlated to the melting temperature Tm,1, 2 the sublimation energy L,,l the heat of fusion Lf,3 crystal structure, and valence.4 Working with mechanical parameters Le claire5 proposed that the activation energy for vacancy migration Qm could be related to appropriate shear moduli. He also proposed that the activation energy for vacancy formation 62, is proportional to Ls. THEORY We consider that Le Claire's expression for 4, is satisfactory. But an alternate expression for Qm in terms of the bulk modulus is just as satisfactory from a theoretical point of view for the prediction of the energy of vacancy migration in pure metals and can more easily be used for alloys. In order for Qm to be a minimum, not only the moving atom but also adjacent and nearby atoms must undergo distortions. These distortions are neither isotropic as is implied by a correlation with the bulk modulus nor unidirectional as implied by a correlation with a shear modulus, but are complex and multidirectional. A complete analysis in terms of the bulk modulus and all the shear moduli is not yet available. In a first approximation in which only one parameter is used, there is no obvious theoretical reason to prefer the shear modulus over the bulk modulus. The bulk modulus is a much more convenient parameter for use in predicting Qm. Shear moduli are known for less than half of the metallic elements while bulk moduli are usually available. Furthermore, because of the directional dependence of shear moduli, their estimation for alloys appears inherently more difficult than is the estimation of bulk moduli. We assume that the bulk modulus Bs reflects an average value of the shear moduli such that the strain energy at the point of maximum distortion of the lattice during vacancy migration can be expressed as

Jan 1, 1964

By G. S. Scott, G. W. Jones

ECONOMIC waste caused by mine fires may become considerable,15 especially if a fire is allowed to spread or temporarily to get beyond control. It is important, therefore, to act promptly whenever a fire is suspected and to make every action count. To contribute toward its extinction effectively it is necessary to know at the earliest possible moment, and continuously thereafter, what is happening at the seat of the fire, which may be in a remote or inaccessible area, and also to recognize what may be expected as a result of any proposed combative measure. In combatting a fire the mining engineer and the chemist should cooperate, first deciding upon the course of action to be taken and then drawing upon the mining engineer's intimate knowledge of the physical structure of the fire area, the cost and time required to carry out proposed operations, and the probable efficiency with which these operations could be performed, and upon the chemist's knowledge for the results to be expected therefrom. After the initial steps to be taken have been decided, it devolves upon the mining engineer to see that they are carried out and upon the chemist to evaluate the results and to keep the mining engineer continuously informed in regard to a variety of matters-such as the composition and toxic or asphyxiating properties of the atmosphere in which the men may be working, whether the fire is increasing or decreasing in intensity and its probable temperature, the quantity of air leakage and the explosion hazards of the fire area. The purpose of this paper is to discuss what the chemist can and cannot contribute as a member of the fire-fighting personnel. The technical literature contains several hundred papers relating directly and indirectly to mine fires, and this fact alone is testimony to the complex nature of the phenomena involved in the birth, life, and final demise of a fire. A fire may be stopped (I) by preventing oxygen from reaching the coal or (2) by removing the conditions necessary for the rapid reaction of coal with oxygen; i.e., decreasing the temperature. All methods of prevention or control. necessarily must be based upon one or the other, or both, of these two principles. . The chemistry of a fire may be understood readily if the low-temperature oxidation of coal is considered as a starting point; then oxidation at higher temperatures (or combustion) ; and with these, the composition of the solid and gaseous products resulting from the oxidation or from the effects of the heat liberated. This discussion refers particularly to Pennsylvania anthracite, although much of the material applies equally well to coals of lower rank. OXIDATION OF COAL Oxidation of coal fundamentally is confined to the surface; that is, the rate at which oxygen penetrates into the interior of a solid block of coal is so slow that it may be ignored.6,16 Oxidation starts when a fresh surface is exposed, and the rate is

Jan 1, 1942

By L. S. Darken

IT has been known for sometime that in an ionic lattice, such as that of Ag2S or FeO, the migration velocity of the anion may differ markedly from that of the cation, the cation being usually the more mobile. It has been shown, for example, that during the formation of silver sulfide tarnish on silver, the tarnish layer grows principally by the motion of silver cations through an essentially stationary silver sulfide lattice. Similarly, the growth of wüstite scale on iron proceeds principally by motion of iron ions, this being accomplished with the aid of vacant iron lattice sites into which the iron may readily move. Likewise investigations of solid solutions of various salts show that there is usually considerable difference in the mobility of the different cations. Measurements of the mobility of various metals in liquid mercury indicate that the various metals move at different rates relative to the mercury. In view of the foregoing it seems reasonable to suppose that when any single phase solution is acted upon by a field, the atoms of different elements respond in different ways; in particular, that the force arising from a particular concentration gradient in a binary alloy would cause the atoms of one component to move with a drift velocity which is in general different from that of the atoms of the other component. The recent experiments of Smigelskas and Kirkendall1 support this viewpoint, since they found, in essence, that during diffusion in alpha brass zinc moves appreciably faster than copper. This was evidenced by the relative motion of inert molybdenum wires. Such a phenomenon is incompatible with the place interchange theory of diffusion proposed by several authors, most recently by Birchenall and Mehl.2 This theory has, however, also been questioned3.4 for other reasons, principally because of the high energy required for direct atomic interchange. The rather large difference between self-diffusivity, as determined by tracer technique, and mutual diffusivity, as determined with the aid of another element at low concentration, might also be interpreted as favoring the above idea; however, Birchenall and Mehl have pointed out that there is another possible interpretation of this difference; this is discussed later. A rather interesting and pertinent observation was made by Schwartz,5 who noticed that tungsten lamp filaments, heated by direct current, commonly fail by necking down in the region at the temperature gradient near the positive end, with a concomitant swelling at the corresponding position near the negative end. He introduces considerable auxiliary evidence to show that this phenomenon is occasioned by the motion of tungsten cations which migrate in the high temperature region from the positive end toward the negative end. The mechanism of this migration is not clearly understood. If, however, this experimental evidence be accepted, we are forced to conclude that alloying elements in the tungsten may migrate by the same or a similar mechanism, whatever it may be, at a greater or lesser rate, thus giving rise

Jan 1, 1948

By J. H. Frye, J. W. Caum

One of the most important methods of increasing the hardness of metals is alloying. In spite of the widespread use of alloys, the fundamental mechanism of alloy hardening is little understood. This is true even of the simplest form of alloy, the primary substitutional solid solution in which solute atoms substitute for solvent atoms at random in the crystal lattice of the latter. A fundamental understanding of the mechanism of solid-solution hardening would be important, both because of the widespread use of alloys of this type and because of the light that might be thrown on the mechanism of hardening in more complicated alloys. The present investigation covers the hardness of primary substitutional solid solutions of zinc, gallium, germanium, and arsenic in copper. All of these are B subgroup elements from the third period of the periodic table. Cu, Zn, Ga, Ge, and As are in groups I, 11, 111, IV, and V, respectively, and lie just to the right of the transition elements. Because of their cost, it is unlikely that Ga-Cu and Ge-Cu solutions will ever be of commercial importance, but the intent of this study has been to discover some of the fundamentals of solid-sdstion hardening and it has been demonstrated that such a study is far more likely to be fruitful if alloys are made up on the basis of position of the constituent elements in the periodic table than if commercially important alloys are used. Many investigations have been made of the hardness of substitutional solid solutions, but lack of attention to purity of the metals, infrequent grain-size control, and the use of varying testing techniques have virtually invalidated any comparisons. The purpose of most investigations has been to solve immediate problems and not to solve the primary problem: Why do solid solutions usually have a greater hardness than pure metals? Previous Work Theories have been advanced to account for the hardness of solid solutions, but relatively little experimental work has been done. Perhaps the first experimental work of merit was that of Norbury1 on copper alloys. He showed that for several alloys there was a correspondence between the hardness of one atomic per cent solutions and atomic volume of the solutions. More recently Brick, Martin, and Anger2 have investigated the effect of various solute elements on the hardness of copper. They concluded that the hardening effect of these solutes depended "primarily on the difference in atomic volume of solute and solvent or, relatedly, upon the parameter change of the solvent or the extent of solid solubility." They also observed the effect of these elements on hardness and texture developed by rolling and by annealing of rolled material. Austin3 examined the hardness and response to heat-treatment of various iron solid solutions. Frye and Hume-Rothery4 measured the hardness of a number of silver solid solutions containing approximately 1 References are at the end of the paper.

Jan 1, 1943

By J. K. Edgar

FOR a number of years the production and use of super-purity aluminum (better than 99.99 pct) has been steadily increasing. High-grade lots of such aluminum show certain outstanding characteristics not found in lower grades containing principally silicon, iron and copper as impurities. One such characteristic is the so-called "self annealing," that is, the recrystallization of the heavily cold worked metal at room temperature.' Interest therefore is aroused as to the effects of the impurities. It is well known that the amounts of silicon and copper which occur in aluminum of better than 99.95 pct are completely soluble, at least at elevated temperatures (above 200°C). Iron, on the other hand, is known to be fairly insoluble in solid aluminum. Thus, a knowledge of the limits of this solubility would be of considerable use in studying the characteristics of the high purity metal. All investigators have agreed that iron has very low solubility in solid aluminum. Rosenhain, Archbutt and Hanson2 reported traces of an aluminum-iron phase in the "purest samples of aluminum obtainable." Gwyer and Phillips3 reported that an iron constituent was visible under the microscope in metal containing ".0088 per cent iron." Roth1 found that in the solid state the solubility of iron in high purity aluminum was 0.01, 0.01, 0.017 and 0.022 pct at 225, 320, 500 and 600°C respectively. Dix5 working with alloys containing less than 0.03 pct impurities, concluded from microscopic and chemical analyses of eutectic areas that the eutectic composition was close to 1.7 pct iron. Dix placed the eutectic temperature at 655°C'. Archer and Fink,6 using high purity aluminum-iron alloys, found that the hypoeutectic liquidus intersects the eutectic horizontal at 1.7 pct. This is in fair agreement with the investigation of the aluminum-iron system by Gwyer and Phillips who placed the eutectic at 1.89 pct iron with a freezing point of 653° PREPARATION AND CHEMICAL ANALYSIS OF ALLOYS Electrolytically refined aluminum (99.991 pct aluminum) and a high purity aluminum-iron alloy (11.45 pct iron) were used in the preparation of the alloys for this investigation. To aid in controlling the iron content of the experimental alloys, an alloy of lower iron content was prepared first from these materials. The high purity aluminum was melted and heated to about 700°C in a plumbago crucible coated with alundum cement and the aluminum-iron alloy was then added. The alloy was thoroughly stirred, fluxed and skimmed and then chill-cast into notch bars. The analyses of the three materials are given in Table I. The alloys for the determination of the solid solubility of iron in aluminum were prepared by melting 600 g total of the aluminum plus the required quantity of the aluminum-iron alloy (No. 92531). These

Jan 1, 1948

By C. E. Lesher

Two processes for agglomerating fine sized ores with low temperature coke are described. One process (Orcarb) agglomerates ores with limited amounts of carbon; the other (ore-carbon pellets) pelletizes fine sized ores, using low temperature cokes as the binder. Data are presented on the products obtained when taconite, magnetite, and hematite concentrates and several titanium oxide ores were used. REDUCTION of finely divided oxide ores has long been a major metallurgical problem. Various methods of agglomerating, notably briquetting, sintering, nodulizing, and pelletizing, have been developed and are in industrial use. Carbon is the usual reducing agent for oxide ores and attempts have been made to agglomerate fine ores with coking coal in order to get the metallurgical advantages of intimate contact and increased particle sizes suitable for subsequent smelting or reduction.1-3 For the past three years, research has been in progress on two processes for combining fine sized ores with reactive carbon in the form of low temperature coke. By one process, designated Orcarb, the ore is coated with coke carbon in amounts limited to that required for reduction and the result is an appreciable but limited increase in product particle size over that of the original ore. The second process, called ore-carbon pellets, produces pellets of fine ore bound by low temperature coke. The first objective was to develop a process for combining an oxide ore with only enough carbon for its reduction, the amount being that derived from the simple reduction equations. The carbon (that amount theoretically required for the reduction of the oxides in an agglomerate with ore), calculated to CO, ranges from 10 pct for zinc calcines Or phosphate Ores to 21 pct for rutile and 26 pct for silica. The carbon required for reducing iron oxides falls between the extremes—10 and 26 pet' When the carbon in the agglomerate is low temperature coke, reduction by hydrogen may be expected to take place, thus modifying the calculated carbon require- ment. On the other hand, in practice, an excess of reducing agent over that required in theory is normally used. Screen sizes of three iron ores on which the greater part of the experimental work was performed are given in Table I. Most of the testing was done with Freeport (Renton Mine) coal, but Pittsburgh and Elkhorn bed coals were also used. The first objective was to agglomerate the ore with sufficient low temperature coke to provide carbon for reduction, i.e., in the range from 10 to 25 pct. This was accomplished by preheating the ore, mixing with pulverized coking coal, and completing the coal carbonization in a plain steel rotating retort. The pilot retort, as it is now constituted, is shown by diagram in Fig. 1 and photograph, Fig. 2. Ore is fed into the upper kiln by a screw; it is heated to 900° to 1100°F by direct flame and it is then discharged into an insulating hopper from which it goes

Jan 1, 1956

By Hong Liang-shi

Olivine lithium iron phosphate (LiFePO4) is considered as one of the most promising materials for lithium-ion secondary batteries because of its high theoretical capacity, low cost, good safety, benign environment and good cycle performance. In this paper, carbon-free and/or carbon-coated olivine lithium iron phosphate composite ultrafine powders were successfully synthesized from aqueous precursor solutions of (NH4)2Fe(SO4)2?6H2O, H3PO4 and LiOH?H2O by co-precipitation method. The obtained LiFePO4 or LiFePO4/C powders were characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). Their electrochemical performance was investigated in terms of cycling behavior. As confirmed by X-ray diffraction and scanning electron microscope, the material obtained by co-precipitation within the temperature range of 60ºC to 100ºC and then followed by moderate heat treatment are a single-phase olivine LiFePO4with the particle size of about 300nm. An improved carbon-coated olivine LiFePO4/C material was prepared by adding conductive carbon materials, such as glucose, activated carbon and acetylene black, into the precursor. The carbon dispersed in the materials increases the electronic conductivity of LiFePO4/C composite, and consequently, leads to high rechargeable capacity of the material. The carbon-coated material with carbon amount of 7.64%wt obtained from glucose has the first discharge capacity of 150.3mAh/g at the rate of 0.1C and 129.3mAh/g at the rate of 1.0C, respectively. After cycled for 50 times, the capacity retention rate is 95.13% at the rate of 1.0C in the voltage range of 2.5 to 4.3 V vs. Li/Li+.

Jan 1, 2006

By G. A. Brooks, R. W. Matusewicz, Nazmul Huda

"A computational fluid dynamic (CFD) model of a conventional tuyere blown slag fuming furnace has been developed in Eulerian multiphase flow approach. The model was developed by coupling CFD with kinetics equations developed by Richards et al. for zinc fuming furnaces. The model integrates submerged coal combustion and chemical reactions with the heat, mass and momentum interfacial interaction between the phases in the system. The model predicts the velocity, temperature field of the molten slag bath, generated turbulence, vortex and coal utilization behavior from the slag bath. The highest coal penetration distance was found to be at l/L = 0.2, where / is the distance from the tuyere tip and L is the total length (2.44m) of the modeled furnace. The model also predicts that 10% of the injected coal bypasses the tuyere gas stream un-combusted and carried to the free surface, which contributes to ZnO reduction near the free surface.IntroductionSignificant metal values are often discarded with slag in the form of metal oxide produced by the smelting industries. These metal values can be recovered from the slag by proper treatment. Zinc slag fuming is such a process, where a reductant source (usually coal) is injected in the molten slag bath to reduce dissolved ZnO from the bath into metallic zinc vapour. The process can be carried out in either conventional tuyere blown furnace or top submerged lance (TSL) smelting furnace. Conventional slag fuming processes are carried out on batch basis in a rectangular tuyere blown furnace. Approximately 50 tonnes of charge (either molten slag or solid slag) is fed to the furnace at the beginning of each fuming cycle. Two opposing sets of submerged tuyeres are employed to inject air and pulverized coal into the molten slag bath to carry out combustion and reducing reactions."

Jan 1, 2012

By C. C. Furnas, T. L. Joseph

It is well known that particles of different sizes are not distributed evenly throughout the average charge in an iron blast furnace. Just how great the disparity in particle size in different parts of a single plane in a furnace may be is indicated by the results of some recent investiga-tion1,2 conducted by the Bureau of Mines on a furnace operating on Lake ores. The wide variations found in gas velocity, gas composition, and temperature from the periphery to the center of the upper charge column were caused by the great variation in particle size of the raw materials used and were also greatly influenced by the methods of charging. This paper summarizes the results of an investigation of the influence of different methods of charging and of the treatment of raw materials upon the size distribution of the solid particles in the blast furnace. A more complete report will appear later as a Bureau of Mines technical paper. Importance of Gas-solid Contact One of the authors has pointed out in a previous report? that the operation of the blast-furnace process is entirely dependent on contact between the gas stream and the solid particles in the stock. The gas stream carries the necessary heat as well as the carbon monoxide molecules that do the work of rednction. In the parts of the furnace in which there is little or no contact between the gas stream and the solids there can be little work of reduction. Obviously, the part of the apparatus that is not doing the work for which it is intended is inefficient; the ideal condition is one in which all portions of the stock column are

Jan 1, 1929

By B. G. Klugh

The present paper represents a preliminary investigation of the ultimate structure of iron-bearing materials which have been subjected to heat treatment for the purpose of agglomerating the fines, or for chemical changes, or for both. Primarily, the object of this inquiry was to determine the relation of the microstructure of each of these materials to its specific susceptibility to the action in the blast-furnace. It is hoped that this small contribution will serve as a nucleus to a line of research that will throw some light upon the debated questions involved in blast-roasting. Thus far the investigation has been conducted along lines of analogy of known principles, rather than through the application of any well-defined system of microscopic petrography. This is obviously due to the fact that we are dealing with ma-terials which are the artificial products of a new art, rather than with the natural materials from which the essence of the pure science has been evolved. In the limited time allowed for this research, it has been conducted upon those materials the chemical content of which allows of their use commercially in the blast-furnace. The following microphotographs are arranged in the order of the degree of complete fusion to which the mass in question has been subjected, in effectively binding the particles together. A very notable fact here clearly demonstrated is that the degree of fusion to which the material has been subjected is inversely proportional to the reducibility of the product. The characteristic of the material under consideration to which reducibility is almost universally attributed call be progressively traced in the following arrangement, through the identity of the obvious microscopic constituent. Furthermore, the degree of fusion to which a bod? has been subjected is recorded in the presence of resultant products of fusion in that body. Such readjustment is generally apparent

Jan 1, 1914