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By Roy A. Lindgren

SINCE the year 1643, when the first blast furnace in America for treating iron ore was built at Saugus, Mass., out of mica schist quarried in the neighboring district, the procurement of a suitable refractory for furnace lining has been a problem of concern to the operators of furnaces. The stacks built of mica schist continued to smelt iron ore until about 1836, when, according to F. H. Norton, the first firebrick were produced', at Queens Run, Pa. Other writers speak of brick having been molded and burned in Massachusetts about the year 1834. In 1841, Andrew Russell began to produce medium refractory plastic clay brick near East Liverpool, Ohio, that were used for lining blast furnaces'. The well-known Kentucky clay-producing district was not opened up until the year 1871, but since then it has produced a large percentage of the linings for iron blast furnaces. While some strides have been made by the refractories industry during the 100 years that have passed since the first firebrick were produced, it has been only during the last two decades that any real progress has been made towards bettering the product, even though the method of production had improved. Perhaps the fault lies with the user of the brick rather than with the producer, for not sooner demanding a supe¬rior product. During the past 15 years the tonnage produced per lining has increased from 500,000 gross tons to 1,000,000 gross tons, and now some furnaces are producing 1,600,000 gross tons and better on a single lining. It is true that enlarged capacity of furnaces and improved practice have accounted for some of this increase in tonnage, nevertheless better quality in firebrick must be given credit for its share. However, we are not yet ready to say that we have reached a maximum life of furnace lining. We believe that a better product can be produced and that the refractories industries of America will, through their extensive research depart-

Jan 1, 1937

By L. F. Mondolfo

An investigation of the relationship between properties of the elements and type of binary diagram formed was conducted. It was found that, for each type of equilibrium diagram, the factors for the size, valence, electronegativity, period, melting point, entropies of fusion, and sublimation calculated for each pair of elements cover a range of values. However, these factors show sufficient relationship to the equilibrium diagram so that the correlation of several of them can be used to predict the type of diagram formed, or at least limit the choice to only a few types. ThE goal of the metallurgist concerned with alloy development has always been to find a method that predicts the properties that can be obtained when a certain metal is added to another one. In most cases a qualitative predictiton of properties can be made if the equilibrium diagram is known. However, this means that for new metals the alloy development has to start with the experimental determination of the equilibrium diagrams. Because this determination is at least as complicated and time-consuming as the determination of the properties themselves, most alloy development has taken place by trial and error, and the study of the equilibrium diagrams has followed rather than preceded the creation of new alloys. Alloy structures and properties depend on the interaction between electrons and a complete knowledge of these interactions would permit prediction of structure and properties of alloys. Unfortunately direct measurement of these interactions is extremely difficult and somewhat doubtful and only properties that depend on them can be measured easily and with certainty. Study of the relationship between properties of the elements and equilibrium diagrams is not new. Besides the well known Hume-Rothery rule of the necessity of an atomic diameter fit within 15 pct for extensive miscibility in the solid, and the wide knowledge of the effect of such factors as size, electronegativity, electron-atom ratio on solid state features,"' work relating to liquid state and liquid-solid reactions can be found in the literature. Of particular interest is the work by Axon,3 who investigated the effect of size and melting point on a selected number of eutectic and monotectic dia-

Jan 1, 1962

By S. R. Titley

The recent emphasis placed upon the use of molybdenum as a geochemical indicator has stimulated considerable inquiry into the behavior of molybdenum in the zone of oxidation. This paper represents a summary of recent and continuing experimental work and calculations in an investigation of a portion of the system Mo-Fe-S-H20 and treats the stability of various iron and molybdenum compounds with respect to oxidation potential and pH. Using experimentally determined free energy values for ferrimolybdite, diagrams of the stability fields of this mineral have been calculated with respect to ilsemannite (?), molybdenite, pyrite and limonite. This theoretical approach is the one utilized by Garrels3'4 in studies of the relationships of various minerals in the zone of oxidation. Use of this approach is particularly suited to the study of geochemistry in the zone of supergene processes because of the low temperatures, low pressures and other relatively easily determined and duplicated factors that exist in the near surface environment. Such a study of molybdenum, however, is complicated by several factors. One of these is the fact that the strong amphoteric behavior of molybdenum makes possible a wide variety of substances and complexes whose exact chemical natures are unknown. The second factor is the dearth of thermodynamic data for many of the simplest of the possible compounds and ions important to the study. For the purpose of this study, the problem of complexes has been approached through considering only the simpler possibilities realizing that the complexes and systems so treated may be gross oversimplifications. All the complexes considered, however, have been suggested in the chemical 2,7,9,12 or geologi-cal literature. EXPERIMENTAL WORK Studies of the behavior of molybdenum ions and ferrimolybdite have been carried out in aqueous sys- tems, and reactions have been followed by simultaneous measurement and recording of pH and oxidation potential. A major problem involved in this study was the long periods of time necessary for equilibrium to be established in some of the systems considered; in a few instances, these periods exceeded four weeks, that is, four weeks during which measured conditions changed continuously. Another problem, in some instances, was the indeterminate nature of the reactions that have taken place. Because of the tendency of molybdenum to complex, reactions which take place under some of the more extreme imposed conditions of oxidation and acidity or alkalinity are unknown. However, useful data for the present work were obtained from studies of the molybdate ion and ferrimolybdite between pH 2 and 8 and under only moderately oxidizing to nonoxidizing conditions. Instruments used in the experiments were a Hewlitt-Packard Model 412A VTVM, a modified Beckman Zeromatic pH Meter and two Varian model 11 recorders. pH was measured between glass and calomel electrodes and Eh was measured between calomel and platinum electrodes. Conditions of pH were varied with 1N H2SO4 and 1N NH4OH and 1N NaOH. Eh was varied with gaseous nitrogen, oxygen or aqueous H202. Ambient temperature was essentially uniform at 24ºC and was increased in the reaction vessel by the positioning of a magnetic stirrer whose temperature was sufficient to bring the temperature to 2S°C in the reaction. The temperatures of reaction did not vary more than 1/2ºfrom 25°C. Two reactions were investigated, the ferrimolybdite-limonite-water reaction and the reduction of molybdate ion. Studies of both reactions yielded useful data that were used in preparation of the Eh-pH diagrams. The traces of the reactions are shown on Fig. 1. Ferrimolybdite-Limonite- Water: Studies of this reaction involved analysis of the solution of ferrimolybdite and simultaneous formation of ferric hydroxide. The data are summarized on Fig. 1. In this reaction, equilibrium was attained at various pH's when coexistence of the two solid phases (ferrimolybdite and ferric hydroxide) was attained. At the proper pH, controlled by the amount of ferrimolybdite and thus the dissolved content of molybdate species, both phases were observed and reaction times to complete the transition were on the order of weeks. The reac-

Jan 1, 1963

By I. R. Kramer

The stress associated with the surface layer was deter-minedfor iron and molybdcnum. These measurements show that the surface layer plays a very important role in the plastic deformation of bcc metals. From the relationship between strain arui the surface layer stress and the back stress imposed by the internal obstacles, it is Proposed that the term of of the Hall-Petch equation is related only THE large number of studies on plastic flow of bcc metals have failed to delineate clearly the nature of the obstacles influencing dislocation movement. Since there have been numerous articles which have reviewed the mechanisms proposed to explain various aspects of plastic flow of bcc metals (for example, conrad1 and Keh and weissmann2), no attempt will be made here to discuss their conclusions. However, it should be to the surface stress while the term Kfd is the stress required to move dislocations through internal obstacles. Further, it was possible to derive the well-known empirical equation C = , and it is shown that the terprz a is comprised of two terms: a term Cs associated with the surface layer stress and Ci related to internal dislocation obstacles. pointed out that in all of these publications it has been tacitly assumed that plastic flow occurred uniformly throughout the cross section of the specimen (except, of course, for the Luders band region), It has generally been further assumed that the nature and distribution of the obstacles opposing the motion of dislocations are of the same type throughout. The role of the surface layer in bcc metals has not, as yet, been considered even though its role in fcc metals has been shown clearly to be of primary importance.3-5 Investigations on fcc metals have shown that at the onset of plastic deformation a surface layer acts to

Jan 1, 1968

By A. C. Fraker, H. H. Stadelmaier

In the systems Mo-Fe-C, Mo-Co-C, and Mo-Ni-C the phase boumdaries of the cubic Ij carbides were determined at 1000°C and the variation of the lattice parameter with composition was measured. In the system Mo-Fe-C a single ternary carbide, Mo3Fe3C, was observed. In Mo-Co-C and Mo-Ni-C two new n phases of the type M12C were found: Mo6C06C and Mo6Ni6C. At 1000°C they coexist with the M6C phases MO3-4,CO3-2C and Mo3-4Ni3-2C, respectively. Mo3C03C and Mo4C02C are not separate phases but parts of a single M6C phase region, and the same is true of Mo3Ni3C and Mo4Ni2C. THE n carbide structure type has been known since it was determined by westgren' in 1933, yet reliable information on phase compositions of this type is ap-parently scarce. The following selection of suggested formulas illustrates the extent of the confusion con-cerning compositions: W2-3Fe4-3C,1W6Fe6C,2 W2_4Fe4-2C,3 (W,Fe)6C,4 Tj.-W4Co2C and nz-W6Co6C,5 n1-W3Co3C and n2-w4Co2C,5 W3C03C and w6Co3C2,7 MO3Fe3C,8n2-M04Fe2C,9 (MO,Fe)6C,4 MO3CO3C,8 n2-MO4CO2C.9 Many of these compositions obviously overlap, some disagree in carbon content. The use of the designations 77, and n2 is not consistent. There is uncertainty whether two carbides M6C coexist or whether there is only one M6C with a wide range of substitution of one metal for the other. The existence of M12C seems questionable altogether if one ignores the results of a neutron diffraction study of W6Fe6C supporting that particular metal to carbon ratio.'' More reliable information is available for the iso-typic oxides studied by Nevitt,11 Nevitt, Downey, and orris," and Meussner and carpenter.l3 That n car-bides and oxides are structurally identical, particularly with respect to the location of the metalloid atom, has been demonstrated clearly by Stadelmaier and Meussner14 and also by Parthe, Jeitschko, and sadagopan.15 Therefore the present paper, which attempts to establish the phase boundaries of n defini-tively for three carbon systems, has implications for the whole family of filled Ti2Ni types. EXPERIMENTAL PROCEDURE The samples were prepared in two stages. Pellets weighing 3 g were compacted from powders of the elements and presintered in a closed tube of fused silica that had been evacuated to lO-4 mm Hg. This was fol- lowed by arc melting the sintered samples under argon. Remelting the button once was sufficient to produce homogeneous specimens. The metal powders had the following minimum purities in wt pct: molybdenum 99.5, iron 99.0, cobalt 99.7, nickel 99.9, graphite 99.94. Carbon determinations by the gas volumetric method were obtained from thirty-one of the one hundred samples in the annealed condition. They were limited to compositions that were critical to placing a boundary line in the isothermal sections. The carbon losses were comparatively low and averaged less than 1.5 at. pct. For annealing, the samples were sealed in tubes of fused silica evacuated to 10-4 mm Hg. The annealing schedule was 20 hr at 1250°C followed by 150 hr at 1000" ±10°C. For the water quench the silica glass tubes were broken mechanically to speed the quench. The specimens were examined in the as-cast and annealed condition by standard metallographic techniques. Some of the as-cast and all annealed samples were studied by X-ray diffraction using a 114.6-mm powder camera with filtered Co radiation. The lattice parameters of the n phases were determined by graphic extrapolation to 8 = 90 deg on a plot against sin2 8. It is estimated that the maximum error in the lattice parameters is ±0.002A.. The phase fields were determined by the disappearing phase method, relying on X-rays for phase identification and on microscopy to detect small amounts of a phase. RESULTS Pertinent information on the binary side diagrams has been summarized by Hansen and Anderko16 and Elliott17 and will not be discussed further. Photomicrographs documenting the equilibria at 1000°C have been selected to avoid redundancy due to the similarity of the three systems. Thus there will be only one picture showing an equilibrium with Mo2C, and so forth. Molybdenum-Iron-Carbon. An isothermal section of most of the Mo-Fe-C system at 1000°C is shown in Fig. 1. No attempt has been made to distinguish between a and y iron or to determine their phase boundaries. A conspicuous absence is the phase Fe2 1Mo2C6 with the Cr23C6 structure, supporting the suggestion by Krainer4 that it decomposes by annealing at high temperatures. The only ternary phase is found in a narrow range around Mo3Fe3C (MO43Fe43C14). A microstructure with a two-phase mixture of Mo + n is seen in Fig. 2. The variation of the lattice parameter of n with the estimated composition is shown in in Table IA. The phase diagram does not agree with the results of Kuo9 who reported n2-Mo4Fe2C. Our lattice parameter Varies from 11.095A at the iron-rich end to 11.140Å at the molybdenum-richoend of the phase field whereas Kuo9reported 11.26Å for Mo4Fe2C. We are in agreement with the older work

Jan 1, 1970

By K. E. Brown, J. P. Brill, T. C. Doerr

A wide range of intermittent gas-lift tests way conducted in a 1,500-ft experimental well through 11/4- and 11/2-in, nominal size tubing. The well was equipped with two gas-lift valves, four Maihak electronic pressure transmitters and surface facilities to measure casing and tubing pressures, temperature, liquid production and the rate and volume of gas injected. For each tubing size, tests were conducted varying the slug length, gas volume injected and liquid viscosity and surface tension. From these tests, an empirical "fallback" or liquid loss correlation has been developed. No general fallback correlation could be obtained, and the correlation is presented in the form of one curve for each slug length of a given liquid and lubing size. A conceptual model has been developed which combines the fallback correlation with equarions which govern liquid slug pow. A mathematical simulation of the model in the form of a digital computer program is used to calculate total recovery, gas volume used and clearance time for a given test. Tubing pressures at the gas-lift valve and at the gm-slug interface are calculated as a function of time. Tubing pressures at the surface during slug clearance ore also calculated. The results compare favorably with the test data and verify the conceptual model. The extent to which the model can be used for other tubing sizes, depths, liquids and gas-lift valves can only be determined with additional experimental data. Data are also necessary so that a fallback curve can be constructed for the particular test conditions studied. INTRODUCTION The flow of liquid slugs in vertical conduits has long been an established production method in the petroleum industry. Under the name "intermittent gas lift", many advances have been made in engineering design. However, the unsteady-state nature of liquid slug flow has discouraged attempts to describe the problem analytically. The result has been that intermittent gas lift is dominated by rules-of-thumb engineering practices developed over many years. The advent of slim-hole completions has increased the demand for a more rigorous solution to the intermittent problem. Small-diameter conduits offer more frictional per intermittent cycle. Small-diameter conduits are defined to be 1%-in. nominal size tubing or smaller. When oil is produced from the reservoir in which it is found, and transported to surface tanks by intermittent gas lift, three separate flow stages are encountered: flow of the fluids to the wellbore through a porous medium, vertical flow of a liquid slug from the point of gas injection to the surface, and horizontal flow of the liquid slug through the surface flowlines from the wellhead to the surface tanks. The three stages are depicted schematically in Fig. 1. The present study deals with liquid slug flow in both the vertical and horizontal conduits, ending when the bottom of the liquid slug reaches the surface. Due to the large number of variables involved, the analytical study of intermittent gas lift is extremely complex. The possibility of flow regimes other than slug type, the nature of the force fields acting on the system, the interfacial instabilities involved, the varying operational principles of existing gas-lift valves and the complete unsteady-state nature of the physical phenomena occurring in an intermittent gas-lift cycle relate some of the difficulties encountered.

By Strathmore R. B. Cooke, Thomas E. Bam

The paper discusses the mineralogy, structure, and strength of magnetite pellets fired in air and in a neutral atmosphere at various temperatures. The information obtained from this investigation is used to explain the origin of the structures occurring in pellets produced by pilot-plant operation. MUCH experimental work has been performed on i-VL the mechanism of agglomeration and pelletiz-ing of moist ore and concentrates and on the process of firing agglomerates, but except for the work of Tigerschiold and Ilmonil much of the published information is empirical, and the literature contains no information concerning the structure of fired pellets. Results of a preliminary study of the micro-structures occurring in pellets produced both in the laboratory and on a pilot-plant scale are presented in this paper. Most of the results were obtained from pellets prepared from Mesabi magnetic taconite, but through the courtesy of the staffs of the Minnesota Mines Experiment Station and the Bethlehem Steel Co., fired pellets produced from limonite and hematite ores and from Lebanon magnetite have also been examined. The work has been restricted almost entirely to pellets produced without additives, the exceptions being those in which coal was added to the filter cake before rolling. Schwartz has described the microstructures occurring in ore sinters produced under reducing conditions.' Many of the structures and constituents he describes are common to fired pellets, but the constituents normally occur in markedly different proportions. His statement that "in all satisfactory sinter the amount of hematite is small, perhaps not over 2 or 3 per cent" is inapplicable to pellets produced by pilot plant operation or by any process in which air is not deliberately excluded. Pilot plant pellets contain over 90 pct by weight of hematite, and those produced in the smaller furnaces of the Minnesota Mines Experiment Station contain more than 80 pct of that constituent. Preparation of Specimens It is difficult to examine unfired pellets microscopically because of their insufficient coherency to withstand sectioning and polishing. Fired pellets sometimes lack coherency and frequently contain holes which are troublesome during polishing. Impregnation of both air-dried and fired pellets is readily accomplished by the use of methyl metha-crylate monomer." The dry pellets are covered in a test tube with excess monomer, to which a small amount of accelerator has been added. When the test tube is placed in a cooling bath and evacuated with an aspirator, most of the entrapped air is removed, and disruption of weak pellets by boiling of the monomer is reduced to a minimum. Polymerization is then effected by immersion of the test tube in a water-bath at about 45"C, this temperature being held for 4 or 5 days. The test tube may then be broken away from the solidified mass and the pellets sectioned by a carborundum wheel or a diamond saw. Where time is important, impregnation is carried out at a higher temperature by Meyer's method.' Air-dried pellets must be impregnated with especial care; otherwise swelling occurs and the solids are displaced. It is more important to be certain that the monomer forms a reasonably complete network throughout the specimen than that all entrained air is removed, and for this reason the vacuum technique may be omitted. Impregnated agglomerated products and pellets are extremely coherent, section well, and may be polished either by hand or by machine. Hand polishing is not satisfactory for the examination of conditions existing at the boundaries of grains, and for this machine polishing must be used. The Graton-Vanderwilt machine gives excellent results, provided that pressure on the specimen is considerably in excess of that recommended by the manufacturer. Mineralogy of Fired Pellets Only two opaque iron minerals, magnetite and hematite, have been recognized in pellets. The complete identity of, these artificial minerals with their corresponding natural counterparts is shown by their mineralographic characteristics and their X-ray structures. Wiistite has not been found. Slag is the most common transparent constituent of fired pellets. Occasionally conditions have been appropriate for the crystallization of fayalite from the slag, and at other times another crystalline sil-

Jan 1, 1953

By Strathmore R. B. Cooke, Thomas E. Bam

The paper discusses the mineralogy, structure, and strength of magnetite pellets fired in air and in a neutral atmosphere at various temperatures. The information obtained from this investigation is used to explain the origin of the structures occurring in pellets produced by pilot-plant operation. MUCH experimental work has been performed on i-VL the mechanism of agglomeration and pelletiz-ing of moist ore and concentrates and on the process of firing agglomerates, but except for the work of Tigerschiold and Ilmonil much of the published information is empirical, and the literature contains no information concerning the structure of fired pellets. Results of a preliminary study of the micro-structures occurring in pellets produced both in the laboratory and on a pilot-plant scale are presented in this paper. Most of the results were obtained from pellets prepared from Mesabi magnetic taconite, but through the courtesy of the staffs of the Minnesota Mines Experiment Station and the Bethlehem Steel Co., fired pellets produced from limonite and hematite ores and from Lebanon magnetite have also been examined. The work has been restricted almost entirely to pellets produced without additives, the exceptions being those in which coal was added to the filter cake before rolling. Schwartz has described the microstructures occurring in ore sinters produced under reducing conditions.' Many of the structures and constituents he describes are common to fired pellets, but the constituents normally occur in markedly different proportions. His statement that "in all satisfactory sinter the amount of hematite is small, perhaps not over 2 or 3 per cent" is inapplicable to pellets produced by pilot plant operation or by any process in which air is not deliberately excluded. Pilot plant pellets contain over 90 pct by weight of hematite, and those produced in the smaller furnaces of the Minnesota Mines Experiment Station contain more than 80 pct of that constituent. Preparation of Specimens It is difficult to examine unfired pellets microscopically because of their insufficient coherency to withstand sectioning and polishing. Fired pellets sometimes lack coherency and frequently contain holes which are troublesome during polishing. Impregnation of both air-dried and fired pellets is readily accomplished by the use of methyl metha-crylate monomer." The dry pellets are covered in a test tube with excess monomer, to which a small amount of accelerator has been added. When the test tube is placed in a cooling bath and evacuated with an aspirator, most of the entrapped air is removed, and disruption of weak pellets by boiling of the monomer is reduced to a minimum. Polymerization is then effected by immersion of the test tube in a water-bath at about 45"C, this temperature being held for 4 or 5 days. The test tube may then be broken away from the solidified mass and the pellets sectioned by a carborundum wheel or a diamond saw. Where time is important, impregnation is carried out at a higher temperature by Meyer's method.' Air-dried pellets must be impregnated with especial care; otherwise swelling occurs and the solids are displaced. It is more important to be certain that the monomer forms a reasonably complete network throughout the specimen than that all entrained air is removed, and for this reason the vacuum technique may be omitted. Impregnated agglomerated products and pellets are extremely coherent, section well, and may be polished either by hand or by machine. Hand polishing is not satisfactory for the examination of conditions existing at the boundaries of grains, and for this machine polishing must be used. The Graton-Vanderwilt machine gives excellent results, provided that pressure on the specimen is considerably in excess of that recommended by the manufacturer. Mineralogy of Fired Pellets Only two opaque iron minerals, magnetite and hematite, have been recognized in pellets. The complete identity of, these artificial minerals with their corresponding natural counterparts is shown by their mineralographic characteristics and their X-ray structures. Wiistite has not been found. Slag is the most common transparent constituent of fired pellets. Occasionally conditions have been appropriate for the crystallization of fayalite from the slag, and at other times another crystalline sil-

Jan 1, 1953

By Ashbel Welch

Gentlemen of the American Institude of Mining Engineers.—As you well know an application is about to be made to Congress, by the American Society of Civil Engineers, for the appointment of a cornmission composed of persons skilled in the production and use of iron, steel, and other structural materials, whose duty it shall be to test the strength, elasticity, and other quatities of such materials ; not simply the substances used as such, but the members of large structures composed of such materials, of the forms and sizes in which they are actually used. As I understand, the papers that will be read here to- night will have for their object to show the necessity for such tests, and therefore the necessity for the commission asked for. As the representative of the Society of Civil Engineers, I have to thank you, gentlemen of the Mining Engineers, for the great zeal with which yon have taken up this subject, and seconded the efforts of the Civil Engineers; or, perhaps I ought rather to say, initiated the efforts to get a suitable commission appointed to obtain most vitally important information which it is admitted on all hands we do not now posses. In drawing up the memorial to Congress, in connection with some of the ablest and best informed of our Society, and in all the discossions on the subject, I have been struck with the emphasis with which the confession is made, that so little is known of the strength of the larger-sized members constantly used in building structures of the magnitude which the present requirements of the country now demand. I presume the remarks made to-night will bring this out very prominently. This is no disgrace, for with the means here-

Jan 1, 1882

By Frederick Laist

THE object of the construction and operation of the 80-ton leaching plant was to test out the leaching of sand tailings on a large scale and, if possible, determine a definite method of operation, and the best construction for the larger unit which is now being built. It was also of importance to obtain some practical data as regards cost items. The 80-ton plant was not expected to be a commercial success. A leaching process on such low-grade material necessitates the treatment of a very large tonnage.. Such a cost item as labor, for instance, is entirely out of proportion in such a small plant. The amounts of acid, salt, scrap iron, and fuel for roasting, however, are the same per ton in an 80-ton plant as in a 2,000-ton plant. These costs were definitely established. Also the percentages of extraction and grade of tailings were definitely determined for a large-sized unit. Following will be found the description of the plant, the method of operation and the results obtained. A -general view of the plant is given in Fig. 1. The bins consisted of one coal bin with a capacity of 30 tons, one salt bin with a capacity of 20 tons, and a "mill tailings" or feed bin which held 70 tons. The coal and salt bins were placed with their floor level even with the firing floor of the roasting furnace. The feed bin, to give it greater capacity, discharged about 12 ft. below this point, to a 12-in. conveyor belt, which, in turn discharged into a pug mill. This fed another conveyor belt, which discharged into the top hearth of the furnace. The furnace was an ordinary six-hearth MacDougall roaster, .20-ft. in diameter. It was equipped with two fire boxes, on opposite sides, the flames entering on the third hearth. An induced draft was obtained with a Buffalo blower, worked as an exhaust fan. Just above the top hearth was an annular flue around the whole circumference of the furnace. Slots at intervals of about 18 in. led from this flue down into the top hearth. The slots were 2 in. wide by 6 in. long. This annular flue proved rather unsatisfactory, as it tended to fill up with flue dust and choke the slots, thus cutting down the draft. The volume of gas through

Jan 8, 1914

By K. A. Svanstrom, W. R. Opie

Problems associated with deposition of titanium infused chloride baths using TiCl4 as a feed material are reviewed. A potentially workable cell design using Alumdum diaphragms is discussed. Problems inherent to diaphragm-type cells are emphasized and experiments described which led to the development of a cell without a diaphragm. INVESTIGATORS assigned the problem of developing a commercial electrolytic process for making titanium metal have found that they are faced with the difficulty of overtaking rapidly improving magnesium and -sodium reduction processes. The ultimate goal must be a simple process that can be conducted with low-cost raw materials in equipment that is inexpensive to build and operate. This paper deals with some work of a preliminary nature conducted by personnel of the Research Laboratories, National Lead Co., Titanium Division. Many others have reported on the general subject of depositing titanium from fused salt electrolytes. A partial bibliography is attached. PRIMARY CONCEPTS Anyone attempting to deposit titanium metal from fused chloride electrolytes using TiC14 as a source material is faced with at least the following problems: 1) Getting the titanium into solution in the bath. 2) Controlling oxidation and reduction reactions associated with multiple valency of titanium, which result in low electrical efficiency. a) Prevention of dichloride oxidizing to trichloride and trichloride to tetrachloride at the anode. b) Prevention of trichloride from being reduced only to dichloride at the cathode. 3) Prevention of metal formation away from the cathode thru disproportionation of titanium dichloride to satisfy the equilibrium. 3 TiCl2 == 2 TiCl3 Ti [I] 4) Protection of reduced chlorides in the bath from reaction with oxygen from the bath container or air. 5) Removing from the bath the deposited metal formed without allowing it to become contaminated with oxygen or nitrogen. 6) Selecting cell materials of construction which will not contaminate the metal product or cause cell inefficiencies. EARLY EXPERIMENTS The initial attempts made to electrodeposit titanium from fused chloride baths using TiCl4 as a source material indicated that TiCl4 was essentially insoluble in molten chlorides of alkali and alkaline earth metals. If, however, the TiCl4 was introduced close to a nickel cathode some metal could be formed and appreciable quantities of reduced chlorides would be present. These reduced chlorides reacted with any oxygen present in the atmosphere above the bath and would also diffuse quickly to the anode (graphite) where they would react with chlorine and be evolved as TiCl4. The net electrolytic efficiency of such a cell is essentially nil. The TiCl4 evolves from the anode at almost the same rate that it is introduced in the vicinity of the cathode although a small amount of titanium metal can be formed on the walls of the cathodic pipe. It becomes apparent from the operation of such a cell that: metal can be deposited on the cathode, although of small particle size and a nonadherent nature, and when reduced chlorides are present in the electrolyte, TiCl4 can be absorbed, probably by the following reactions: TiCl4 + TiC12 - 2 TiCl3 [21 2 TiCl3 + 2 faradays - 2 TiC12 + C12 [31 DIAPHRAGM CELLS These facts encouraged the development of cells containing diaphragms to prevent migration of reduced chlorides from the cathode area to the anode. Small-scale cells for process development are described by Alpert, Schultz, and Sullivan.20 A larger brick-lined cell incorporating internal heating by passing ac through the bath is shown in

Jan 1, 1960

By F. E. Bash

Constantan is an alloy of copper and nickel that is extensively used, under a number of trade names, as a resistance wire with a low temperature coefficient of resistance, and one of the elements of base-metal thermocouples, iron usually being the other thermoelement, although for low-temperature work copper is also used. Before the war, constantan was imported, in common with many other technical necessities. Since it required considerable time to receive the constantan after it was ordered, fairly large stocks were kept on hand; but after the beginning of the war no more was imported and the stocks of foreign material were exhausted about the same time that the steel and munition manufacturers began to need great quantities of it for thermocouples for the heat treatment of steel. To meet this demand, the International Nickel Co. began manufacturing constantan that met all the requirements of the users of resistance wire but did not give the same electromotive force against iron as the German material and consequently could not be used with instruments calibrated for a definite e.m.f.-temperature relation. It so happened that all the constantan made had an e.m.f. lower than that necessary to meet the specifications of the Leeds & Northrup Co. for whom this investigation was carried out. If some had been higher and some lower, good wire could have been obtained by a process of selection, but as it was no wire at all could be procured. To remedy this situation, a thorough investigation was started with the close cooperation of the International Nickel Co. and the Electrical Alloys Co. The specifications to which the constantan had to conform were that it should give an e.m.f. of 47.40 millivolts against pure iron at 1500" F. (816" C.) with the cold-junction temperature at 0" F., or a proportional e.m.f. at temperatures near 1500" F. The method of checking a wire was as follows: It was first welded to a piece of iron wire; Armco iron was found to be satisfactory but iron with greater than 0.1 per cent. carbon would give a lower e.m.f. against the same piece of constantan than pure iron. The couple was then insulated and the fire end was tied to the

Jan 1, 1921

By Roy J. Greenfield, Charles H. Stoyer

A geophysical survey was made in Kylertown, Pa., in an area where the ground water is polluted with acid mine drainage. Since acid mine water is a good electrical conductor, both direct-current electrical and electromagnetic loop methods were examined for their ability to determine the subsurface electrical conductivity structure and from this to imply the location of the acid water. Consistent results were obtained with the two methods and the interpreted subsurface resistivities were consistent with the electrical resistivity measured for water samples. It was demonstrated that fracture traces which act as conduits for ground water flow can be located with electromagnetic surveying methods. Thus geophysical methods for measuring subsurface electtrical resistivity can be used to advantage for monitoring the environmental impact on the ground-water system of acid mine water.

Jan 1, 1977

By J. E. Dorn, S. K. Mitra

The low -temperature tensile and creep behaviors of single crystals of copper were evaluated and analyzed in such a manner as to provide an estimate of the separate contributions of short-and long-range stress fields to strain-hardening. Furthermore, the average force-displacement diagram for thermally activated intep-section of two dislocations was estublished. This diagram plus a knowledge of the variation of dislocation spacing and the long-range back stresses with strain permits on accurate prediction of creep rates. The calculated activation energy for intersection under conditions of a constant strain rate increases linearly with the absolute tempevatus-e as required by theory. AN understanding of the detailed mechanisms for strain hardening constitutes one of the principal unsolved problems in dislocation theory. Two major models for strain hardening have been advanced in the past. The one that has received greatest attention assumes that strain hardening arises exclusively from long range interaction stresses between moving dislocations and piled-up arrays of blocked dislocations on the slip planes. This type of interaction was first announced by Taylor' who revealed that the back stress fields due to a simple uniform array of positive and negative dislocations entrapped in the deformed crystal would result in parabolic hardening. Shortly thereafter Andrade and Henderson" demonstrated that the strain hardening of fcc single crystals was not parabolic, as previously thought, and finally it was recognized that a typical stress-strain curve consisted of three successive stages of deformation, niz., the easy glide, Stage I, linear hardening, Stage 11, and the parabolic hardening, Stage 111, ranges. The objections to Taylor's somewhat na'ive model, which were presented so forcefully by cottrell; were largely removed by the more realistic details incorporated in Mott's analysis.5 But because Mott's theory for hardening via long range stress fields gave somewhat analogous results to that of Taylor's (inasmuch as it also predicted a parabolic rate of strain hardening whereas the observed rate of strain hardening in Stages I and I1 were linear), it was not widely accepted. Major consideration was therefore given to models, such as those which were advanced by Friedel and seegere that were formulated for the ad hoc purpose of yielding linear rates of strain hardening. The second major thought regarding strain hardening is based on the concept that it arises principally from short-range stress fields due to the interactions between intersecting dislocations. Cottrell and stokes7 showed, several years ago, that the constancy of the flow stress ratio at two temperatures regardless of the strain was inconsistent with the concept that strain hardening arose exclusively from long-range back stresses. The argument that strain hardening was primarily due to local interactions of intersecting dislocations was presented in considerable detail by asinski.' Extending Basinski's method of analysis of the intersection process, Mitra, Os-borne, and dorn recently demonstrated that indeed the strain hardening in aluminum single crystals arises principally from local effects coincident with intersection; however, these conclusions, too, must be modified, as will be shown later in this report. The present investigation, devoted principally to the low-temperature deformation of copper single crystals, was initiated in an attempt to ascertain whether or not the same conclusions arrived at for aluminum also apply to metals, such as copper, which have much wider stacking faults. It was soon observed that the strain hardening in copper could not be attributed exclusively to local effects between intersecting dislocations. Previously no analytical method for arriving at the possible simultaneous contributions of long-range stress fields and localized forces on intersecting dislocations was available; consequently, the separation of these two factors could not be readily accomplished. In the present report a method of estimating the separate contributions of each of these two factors to strain-hardening will be presented. The authors will show that both long-range stress fields of the type contemplated by Seeger and Friedel as well as short-range forces of the type considered by Basinski are responsible for strain hardening in fcc metals at low temperatures. This method of analysis also accounts for, in a satisfactory way, the effect of stress, temperature, and strain on the creep rate under constant stress. Furthermore, in the course of presenting their methods of analysis the authors will also reveal the rather complete agreement of their experimental data with the concepts of the theory for thermally activated intersection of dislocations. INTERSECTION MODEL As shown by seegerl0 the strain rate arising from thermally activated intersection of dislocations is given by

Jan 1, 1962

By David W. James

DURING a recent investigation of the transition from a planar to a nonplanar solid/liquid interface for the systems H20-NH4F and 0-AIR,' an apparatus was developed which enabled the morphology of the ice-water interface to be examined during the transition. The slightly curved interface was viewed at a glancing angle with a Bausch and Lomb X30 stereomicro-scope. The interface was obliquely illuminated by a polarized light source. It was thus possible to differentiate between small projections or depressions at the interface, both by a shadowing effect and by the way in which they distorted the colored interference fringes across a particular crystal surface. Many attempts were made to photograph the various stages of interface breakdown. Unfortunately, the limited depth of focus of the microscope rendered the system unsuitable for photographic recording. Visual examination, however, was facilitated by continuous adjustment of the microscope focus control. The following observations of the interface transition were recorded for dilute solutions of ammonium fluoride in water. They are compared with iller's postulated morphologies shown in Fig. 1. i) The initial departure from planarity was characterized by the appearance of a large number of small depressions or "pores" in the interface. ii) The pores were arranged in wavy rows all lying roughly in the same direction within a particular grain. iii) The pores did not appear to form near to grain boundaries. iv) The pores appeared in certain grains before others. v) The transition from the pore structure to the elongated cell structure, Fig. l(d), was difficult to follow. It occurred quite rapidly and no truly irregular cell structure, Fig. l(c), was noticed. vi) The elongated cells gradually became more uniform in size and shape, with straight cell boundaries. They remained elongated, however, and no regular hexagonal cells were observed, cf. Fig. l(e). Several conclusions may be drawn from these observations. Firstly, the appearance of a poxed or, more accurately, a pore structure can be used as a criterion for the onset of constitutional supercooling. Care should, of course, be taken to distinguish between the true pore structure and artifacts caused by splashed-back liquid, particles of oxide, or inefficient decantation of liquid retained between cell boundaries, as described by Spittle et al? Secondly, and contrary to the suggestions of Tiller el l., it seems that interfacial perturbations are characterized not by curved projections but by small depressions or pores. A recent independent investigation by Biloni, Bolling, and cole5 reported in this issue indicates that the depressions might be explained in terms of dislocations intersecting the solid/liquid interface. It is possible that the dislocation concentration is reduced in the vicinity of grain boundaries. This would then explain the grain boundary depleted areas noted in (iii) above. This work was partially supported by the Air Force Office of Scientific Research, Contract No. AF 49-(638)-1029.

Jan 1, 1967

By Robert W. Zimmerman

POROUS SOLID COMPRESSIBILITIES There are four different compressibilities associated with porous solids, each relating the fractional change in either bulk volume or pore volume with the change in either pore pressure or confining pressure. These will be referred to as Cbc, Cbp, Cpc, and Cpp, with the first subscript denoting the relevant volume, and the second subscript denoting the relevant pressure. They are defined as: [ ] Note that minus signs are included in two of the definitions so that each of the compressibilities will always have a positive value. In general, each compressibility depends on the elastic moduli of the matrix material, the porosity, and the exact geometry of the pores. Taking the latter factor into account calls for separate analysis for each different pore shape, which of course can only be attempted for a few relatively simple cases. But lower bounds for each of the four compressibilities can be found, independant of pore structure, in terms of only the porosity (0) and the elastic moduli of the matrix material (any pair chosen from K, E, G and V). The first step is to find relationships between the four compressibilities, starting with the following observation: If a porous solid made of a linear elastic, isotropic and homogeneous matrix material is subjected to uniform hydrostatic pressure of magnitude P on its external and all of its internal (pore) surfaces, the state of stress in the solid will be exactly the same as that which would occur

Jan 1, 1982

By H. E. Hostetter

Grossmann's method1 for calculating the hardenability of steel from the composition and grain size has gained wide acceptance, and when properly used, has been well proved in practical application, both for estimating the hardenability of known compositions and for selecting compositions to meet known hardenability requirements. The Grossmann method uses as the criterion of hardenadility the "ideal critical diameter," DI, which is the' size round that will just harden to a structure of 50 per cent martensite at the center when given the theoretically fastest quench, or "ideal quench." The DI can be related to actual quenching practice if the severity of quench is known; or the DI can be correlated with hardenability as determined by the Jominy end-quench method.2 The effect on hardenability of each element present in a steel can be represented by a multiplying factor, the value of which depends on the amount of the element present and the degree of effectiveness of the particular element. (The value of the factor for a given carbon content varies with the grain size.) When the factors for all elements present in a steel have been determined from charts, they are multiplied, and the resultant product is the DI of the steel. The validity of Grossmann's scheme of multiplying factors has been confirmed in a number of other investigations.3-6 It can be appreciated that a certain desired level of hardenability can be obtained by adding chromium, molybdenum, nickel and vanadium to a base composition containing carbon, manganese, silicon and the usual impurities. Many of the ranges of hardenability used commercially can be obtained by any of the foregoing alloying elements used singly in the base composition. The same hardenability levels also can be obtained through use of any of a great number of multiple element combinations of these alloying elements. In this report a method will be presented for determining what one combination is the most efficient (based on hardenability and cost of added alloy) for a given level of hardenability. It should not be assumed from the emphasis given to hardenability, that hardenability is the only criterion for the selection of an alloy composition. Such properties as the hot-working characteristics, machinability, carburizing characteristics, amount of distortion during quenching and the retention of austenite may be considerations of importance in many applications. However, hardenability is one of the most important properties of an alloy steel and one that must be considered in almost all cases involving heat-treatment by quenching. Therefore, a method for determining the lowest-cost alloy combination should be of considerable value. Determination of Most Efficient Combinations For comparing the alloying elements on standards of cost and hardenability, it

Jan 1, 1947

By H. E. Hostetter

Grossmann's method1 for calculating the hardenability of steel from the composition and grain size has gained wide acceptance, and when properly used, has been well proved in practical application, both for estimating the hardenability of known compositions and for selecting compositions to meet known hardenability requirements. The Grossmann method uses as the criterion of hardenadility the "ideal critical diameter," DI, which is the' size round that will just harden to a structure of 50 per cent martensite at the center when given the theoretically fastest quench, or "ideal quench." The DI can be related to actual quenching practice if the severity of quench is known; or the DI can be correlated with hardenability as determined by the Jominy end-quench method.2 The effect on hardenability of each element present in a steel can be represented by a multiplying factor, the value of which depends on the amount of the element present and the degree of effectiveness of the particular element. (The value of the factor for a given carbon content varies with the grain size.) When the factors for all elements present in a steel have been determined from charts, they are multiplied, and the resultant product is the DI of the steel. The validity of Grossmann's scheme of multiplying factors has been confirmed in a number of other investigations.3-6 It can be appreciated that a certain desired level of hardenability can be obtained by adding chromium, molybdenum, nickel and vanadium to a base composition containing carbon, manganese, silicon and the usual impurities. Many of the ranges of hardenability used commercially can be obtained by any of the foregoing alloying elements used singly in the base composition. The same hardenability levels also can be obtained through use of any of a great number of multiple element combinations of these alloying elements. In this report a method will be presented for determining what one combination is the most efficient (based on hardenability and cost of added alloy) for a given level of hardenability. It should not be assumed from the emphasis given to hardenability, that hardenability is the only criterion for the selection of an alloy composition. Such properties as the hot-working characteristics, machinability, carburizing characteristics, amount of distortion during quenching and the retention of austenite may be considerations of importance in many applications. However, hardenability is one of the most important properties of an alloy steel and one that must be considered in almost all cases involving heat-treatment by quenching. Therefore, a method for determining the lowest-cost alloy combination should be of considerable value. Determination of Most Efficient Combinations For comparing the alloying elements on standards of cost and hardenability, it

Jan 1, 1947

By M. H. Pilkuhn, H. Rupprecht

p layers on n-type substrates of GaAs were prepared by difhsion of zinc into these substrates. Experimental details about the diffusion technique will be presented. It will be shown that inhomogeneity in the substrate doping level and crystal shucture defects cause nonplanarity in the junction plane. These nonplanarities give rise to high threshold current densities. From incremental sheet-conductivity measurements the zinc profile is derived. Data about surface concentration and gradient of the zinc concentration at the junction are presented. Finally, some results of laser diodes, which were made of wafers with extremely planar diffusion fronts, are discussed. ThE investigations reported here are part of a program concerned with the materials aspect in the fabrication of GaAs laser diodes. This includes studies of the influence of crystal defects introduced both during the growth of the crystal and as a consequence of subsequent diffusion. Compared with the progress made in the investigation of structure defects, for instance by X-ray microscopy in materials like silicon, no similar results are known so far for the case of GaAs. The further progress in laser diodes will depend very much upon our knowledge of these structure defects and subsequently upon our ability to avoid them. Laser diodes of GaAs had been made mostly by diffusing an acceptor impurity, normally zinc, into an n-type substrate. This procedure was found more convenient than the inverse one for various technical reasons. We will follow this line and restrict ourselves to zinc diffusion only in this paper. DIFFUSION TECHNIQUES AND EXPERIMENTAL DETAIL In order to set a refgrence for our experiments, we used a standard procedure for the diffusion runs. The diffusions were carried out in a sealed quartz tube for 2-1/2 hr at 850°C. One milligram zinc arsenide (ZnAsz) per cu cm of the tube volume served as zinc source. Under these conditions the junction depth was between 25 and 30 p. It is assumed, according to the investigations of the zinc arsenide system by V. Lyons and V. ilvestri,' that ZnAs2 dissociates completely at 850°C into ZnsAsz and Asg. Since there is a condensed phase of ZnsAs2 in the tube at 850°C, the partial pressure of zinc is controlled by the pressure of the arsenic formed by the dissociation of ZnAs2. Due to the fact that the zinc partial pressure resulting from the dissociation of ZnsAsz is only a weak function of the partial pressure of arsenic, the amount of the initial ZnAs2 is not very critical. Experimentally, we found that the junction depth, as well as the surface concentration, was practically the same, if the ingots of ZnAs2 varied between 0.2 and 5.0 mg per cu cm. The wafers were oriented with the main faces in (100). Surface damage due to cutting and lapping was removed by a chemical-etch treatment in a rotating beaker (etch solution: HzSOr, H202, and HzO in a ratio 3:l:l). The GaAs substrate material was n type and doped with tellurium, selenium, silicon, or germanium. It was grown by means of horizontal or Czochralski techniques. After the diffusion process, junction depth and planarity were checked either by grooving with a

Jan 1, 1964

By Erwin S. Sperry

Some time ago, the author had occasion to make an alloy of equal parts of nickel and aluminum, for the purpose of adding small amounts of nickel to pure aluminum. The nickel was melted in a plumbago crucible under a layer of borax ; and at a proper temperature the aluminum was added, and the whole mass was stirred with a plumbago stirrer. The alloy immediately became incandescent and boiled. It was then poured into iron moulds, in the form of ingots weighing about 10 pounds. The metal when poured was very fluid and free from the viscosity so often noticed in nickel and nickel-alloys. The color of the alloy is gray, not unlike that of wrought-iron, and the fracture is devoid of any crystalline appearance. It is quite brittle, and can be readily ground to a powder in a mortar. More metal was made than was needed; and what remained unused was placed in a covered wooden box and set away. In about three months, as it mas again necessary to use the alloy, the box was opened; and, much to my surprise, nothing but a dark gray powder was found in it. This condition of the alloy could not be accounted for. An attempt was made to melt the powder and pour it again into ingots, but with negative results. Analogy pointed to disintegration; and it was decided to make a fresh sample of the alloy, and watch the material from the beginning. In the second experiment the conditions were identical with those of the first, with the exception that fluor spar was substituted for the borax. This change was made because it was thought that perhaps the borax might have been

Jan 1, 1900