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By E. A. Gulbransen, W. S. Wysong

THE behavior of molybdenum and its surface oxides in oxidizing and reducing gas atmospheres and in high vacua at elevated temperatures is a question of scientific and technical importance The use of molybdenum as a metal or as an important component in alloys in oxidizing atmospheres at elevated temperatures has been limited because of the unprotective nature of its oxide film and the volatility of this oxide at moderate temperatures. This communication will present results of a vacuum microbalance study 1,2 of the following problems. (11) the oxidation kinetics in the temperature range of 250° to 450°C; (2) the reduction with pure hydrogen of thin oxide films formed on molybdenum; (3) the volatility of the thin oxide films, and (4) the vacuum oxidation of molybdenum at high temperatures. Molybdenum is an interesting metal to study for the following reasons: (I) although the oxide-to-metal-volume ratio is greater than one, the metal is not considered protective; (2) the metal oxidizes readily at temperatures of 250°C and higher; (3) the oxides of the metal are reduced at temperatures as low as 500°C by pure hydrogen; (4) the oxide MoO3 melts at 795°C; and (5) the oxides of molybdenum are volatile at moderate temperatures. The following variables are studied in the oxidation kinetics. time, temperature, pressure, surface preparation, surface area, concentration of inert gas in the lattice, cycling procedures in temperature, vacuum effect and high temperature vacuum oxidation The general interpretation of many of these factors has been previously discussed. LITERATURE The oxidation of molybdenum has not been studied critically. Although" many studies have probably been made on the kinetics of the oxidation process, none has been reported in the literature available to us. The crystal structures found in the oxidation of molybdenum have been studied by Hickman and Culbransen 4 Their results showed that MoO2 is the oxide which is stable in contact with the metallic subgtrate throughout the temperature range 300 to 700°C. As the film thickens in the low temperature range, MoO3 becomes predominant on the surface. Above 400°C, Mo03 is no longer observed, Mo02 being the only oxide found. Hagg and Magneli5 have shown from an X ray study that the a-phase, orthorhombic MoO3 is stable up to 1050°C. Two other phases, ß and ß', with compositions close to Mo02 90 are also obtained The formula for the ß phase is not given but that of the ß' phase is defined as Mo9026. The ß' phase is found to be built upon a monoclinic unit cell. A -?-phase is isolated from a preparation M00275 heated for 17 hrs at 670°C. This phase is

Jan 1, 1947

By Sylvan Z. Beer

The factors that determine the yield and crystal size in the two-temperature synthesis of A lp were examined. Low yields and small crystals were associated with low temperatures and pressure. Attempts to grow large crystals in the critical and supercritical region of phosphorus were unsuccessful. Crystal size increases markedly at elevated temperatures. Crystals grown at temperatures as high as 1450° C fluo-resced, under uv excitation, at energies close to the estimated band gap of about 2.4 ev, while crystals grown at lower temperatures tended to fluoresce in the red region of the spectrum. Those grown in the supercritical region showed no ALP fluorescence. Heating the high-temperature-grown ALP under vacuum greatly increased its fluorescence efficiency and moved the emission peak to higher energies. I HE III-V compounds, with few exceptions, have been prepared by the two-temperature method. In its classic form this technique is applicable to closed systems where at least one of the components, in this case the column V element, is a liquid or a solid with a high vapor pressure. One advantage of this method over flow systems is in its simplicity. In addition, because it is a closed system, it can, under the circumstances to be described later, be run at higher pressures of the volatile species than in flow systems. In instances where the III-V compound is soluble in the parent III metal to about 1 mol pct or higher, solution growth can be made to take place by slow cooling. This, for instance, is one way in which single-crystal GaP1 and Inp2 have been grown. Initial attempts to synthesize and grow A1P by this technique were not too successful; the yield was low and the crystals obtained were exceedingly small. The conditions required for improving the yield and growth by this technique were, therefore, sought. Two obvious conditions which could be controlling were examined. These were the temperature of the aluminum and the pressure of the phosphorus. The range of temperatures studied extended from about the melting point of aluminum, 660° to about 1450°C. The latter is dictated by the vapor pressure of aluminum which reaches about 1 Torr at that temperature and the limitations of the materials of construction as described in the next section. The pressure range of interest covers from below 1 atm to above the critical pressure of phosphorus, 82.2 atm. EXPERIMENTAL The Temperature of Aluminum as a Variable. A series of experiments were run in the conventional two-temperature manner. All refractories and quartz were dried by heating at 800° to 900° for a minimum of 24 hr, and usually much longer, before use. The aluminum

Jan 1, 1969

By Edwin T. Myskowski, Alfred H. Hesse

The development by the U. S. Bureau of Mines of a process for purifying manganese by electrolysis has stimulated interest in manganese alloys. While recent publications have shown some alloys of manganese and copper to possess rather unusual properties, none have included information on tensile properties, which have an important bearing on the usefulness of the alloys. Manganese-copper alloys can be heat-treated, since the single phases that exist at high temperatures may be retained by quenching. According to Persson,1 when quenched alloys containing from about 30 to nearly IOO per cent manganese are reheated, alpha manganese is precipitated (Fig. I). Calculations based on Persson's X-ray data indicate that this decomposi-tion is accompanied by a change in volume of as much as ; per cent. The reason that this large volume change has not been noted probably is the slow rate at which equilibrium is reached by these alloys. In an investigation on hardening by cold-work and heat-treatment, Dean and Anderson3 found that quenched alloys increase in hardness with manganese content and that high-manganese alloys harden very slowly with cold-work, while high-copper alloys harden much more rapidly. Heat-treatment has little effect on manganese-copper alloys containing less than 40 per cent Mn, and affects those alloys containing more than 40 per cent in accordance with their manganese content and heat-treating temperature. Dean and Anderson4 also found that cold-work increased electrical resistance of alloys containing from 50 to 80 per cent Mn, and that heat-treatment of alloys containing from 40 to 96 per cent Mn altered the electrical resistance considerably. Dean, Anderson and Potter6 have shown that the high vibration damping capacity that characterizes manganese-copper alloys containing 40 to go per cent Mn is affected by cold-work and heat-treatments. Highest vibration damping capacity at low stresses was obtained by heating for 2 hr. at 450°C. (842°F.) after quenching from solution temperatures. Preparalion of Alloys.—The alloys for these tests were melted in a 17-lb. basic-lined high-frequency induction furnace using electrolytic manganese, grade A ingot copper and a 70-30 CU-Mn master alloy (69.80 per cent Cu, 0.12 Fe, 0.04 Si, 0.006 S, 0.07 C, balance Mn). The manganese was heated slowly to expel excess dissolved gases and melted before the addition of copper. No fluxes or covers were used. The melts were cast in tapered iron molds and the ingots were reduced go per cent when forged to 1/2-in. rounds. These rods were given 2-hr. solution treatments at temperatures that depended upon the composition (Table I). Tensile Tests.—The tensile specimens, 0.313-in. diameter (1.25-in. gauge length),

Jan 1, 1942

By Frank G. Norris, William C. Marshall

The term "total operation" is meant to include problems that cannot be answered from the standpoint of either the blast furnace or the open hearth separately but must be studied by considering the interrelations of these two processes. There are other ways of expressing this idea, such as reference to the blast furnace and the open hearth as an integrated process or by emphasizing the interrelation and interaction of the two processes. Much progress has been made in metallurgy and other fields by breaking complicated processes and reactions into simpler parts and studying each of these intensively. This intensive study frequently is done under the controlled conditions of the laboratory experiment. The entire process is understood better by this specialized study of each of its parts. This procedure is so satisfactory that an understanding of unit operations is a fundamental requirement of chemical engineering. Much discussion of the open-hearth process is in terms of one heat or one furnace. By this is meant that the conclusions apply to one furnace, wherever it may be. Furnaces seldom occur singly; they are located in groups and these groups are located in steel plants having characteristic blast-furnace equipment. Problems that are affected by the number of furnaces operating, by the number of blast furnaces in the plant and by the fact that the open- hearth shop is dependent on the bla furnace capacity rather than on its o needs for the amount of iron available among those which, in contrast to "u operations," we have chosen to call "to operations." Many of these problems, such as cha ing delays and the general mechani problem of material handling, are familiar that merely to define " total op ations" brings them to mind. These pr lems are of such importance that alrea they have received careful thought 2 study and probably will merit furt study. As will be shown later, these mechan problems are so intimately related metallurgical problems of total operati that the effect of certain changes cannot ascribed with certainty to either a mech ical or a metallurgical cause entirely. Although the problems coming under general term of "railroading" are inclu in the problems of total operations, ' others are selected for the discussion of paper, One of these is strictly a problem composition; the other is strictly a prob of tonnage production. The problem of phosphorus is pres whenever basic open-hearth slag is used the blast-furnace burden. This practice not secured universal acceptance chi because of difference in preference for h manganese or low-manganese pig iron hjgh-manganese (2.00 per cent) iron is to made, open-hearth slag as a source manganese is usually cheaper than m

Jan 1, 1943

By Willis R. Battles, William F. Cerini, P. H. Jones

A test for determining the plugging characteristics of an oil-well injection water has been developed. It consists in measuring changes of the filter rate of a water at constant pressure with cumulative throughput when passing the water through a medium grade sintered glass disk. Application of the test method was made to the water used in the Union Oil Company's experimental water flood of the Chapman zone in the Richfield field, Orange County, Callfornia. This water developed increasing plugging tendencies upon aging, even though the finished water from the plant filter exhibited few such characteristics. The plugging material was found to consist of calcium carbonate, ferric hydroxide, and organic substances that were presumed to be bacterial. Various method of stabilizing this water to prevent the formation of plugging material were attempted. Lowering the pH to approximately 6.4 by injecting carbon dioxide provided a moderately satisfactory means for stabilization but a better method of stabilizing this water was found to be first aging and then filtering. Introduction An experimental water-flood project was started on the Chapman zone of the Richfield field in March 1944 and has been described in a previous paper.' It consists of a single injection well drilled between old producing wells. A water-treating plant using primary alum flocculation, sedimentation and chlorination followed by secondary flocculation, sedimentation and fltration is employed to process the water before in@ion. In all of the water-treating operations, the system is open to the air, and no attempt is made to prevent the loss of carbon dioxide or absorption of oxygen by the water. The clear water is stored in a covered concrete basin and pumped through a Transite line to the suction of a high-pressure pump at the injection well' The high-pressure tubing in the well to the injection zone is cement lined. The untreated injection water is a mixture produced with the oil from the Chapman and Kraemer zones and is supplied from the disposal system. Because the injection well was relatively deep (injection zone about 3400 ft.) and would be expensive to replace, it was believed imperative to supply a nonplug-ging injection water and to develop laboratory procedures for evaluating the treated injection water with respect to its formation plugging properties. This report describes the development and application of the test procedure based on the assumption that the plugging properties could be determined by measuring the progressive decrease in flow rate of the water through a porous medium. If the quality of the injection water was good enough so that the plugging action on the porous medium was of small magnitude, it was reasoned that the tendency to impair flow in the formation would not be serious.

Jan 1, 1946

By Walter E. Duncan

The ores treated at the concentrating plant of the Mahoning Mining Co. at Rosiclare, Ill., come largely from the blanket replacement deposits of the northeastern part of Hardin County, Illinois, and consist of complex mixtures of galena, sphalerite and fluorspar in a gangue of quartz, limestone and sandstone. The several minerals are so intimately inter-grown that they are not liberated at the sizes usually treated by gravity concentration in the usual fluorspar plant. For this reason, an all-flotation method of concentration was developed in cooperation with the station of the U. S. Bureau of Mines at Rolla, Mo.1 This flotation separation made possible the commercial production of four coyentrates: (I) lead, (2) zinc, (3) acid-grade fluorspar and (4) metallurgical-grade Auorspar.2-3 Although fluorspar had been floated in Canada in 19214 and a plant at Rosiclare had been floating fluorspar since March 1929, fluorspar flotation was given considerable impetus by the Mahoning developments, since some features of the separation were quickly adopted by other fluorspar companies. The Bureau of Alines5 reports that in the 10 years preceding 1938 only 50,552 tons of fluorspar flotation concentrates were produced in the United States. The rise from this almost nominal figure to 153,750 tons (largely acid grade) in one year (1944)6 is indicative of the activity in fluorspar flotation occasioned by the war. The industry thus proved to be in a position to expand and keep up reasonably well with the requirements imposed upon it by such developments as occurred in high octane aviation gasoline alkylation, in the use of Freon as a refrigerant and as carrier in the Aerosol "bug bomb," and in the atomic bomb project as well as in the expansion of other activities requiring hydrofluoric acid; for example, the aluminum industry. Despite the fact that the greater portion of acid-grade fluorspar produced in the last few years went directly into war uses, the future of the acid-grade field still appears bright. As a result of the activity in fluorine chemistry during the war, it seems likely that in the relatively near future almost every phase of human endeavor will find some fluorine compound involved. The other three concentrates produced deserve some attention in these introductory remarks. The lead concentrates first produced contained both zinc and fluorspar but these did not interfere with their marketing. As will be pointed out later, the quality has steadily improved until today it is a relatively high-grade product. Although some zinc smelters accept concentrates containing limited quantities of fluorspar, it is a very objectionable impurity. Since flotation methods fail in the complete removal of the fluorspar, chemical methods were developed for

Jan 1, 1948

By Walter E. Duncan

THE ores treated at the concentrating plant largely come from the blanket replacement deposits of the northeastern part of Hardin County, Illinois, and consist of complex mixtures of galena, sphalerite and fluorspar in a gangue of quartz, limestone and sandstone. The several minerals are so intimately intergrown that they are not liberated at the sizes usually treated by gravity concentration in the usual fluorspar plant. For this reason, an all-flotation method of concentration was developed in cooperation with the station of the U. S. Bureau of Mines at Rolla, Mo.1 This flotation separation made possible the commercial production of four concentrates: (I) lead concentrates, (2) zinc concentrates, (3) acid-grade fluorspar concentrates and (4) metallurgical-grade fluorspar concentrates.2,3 Although fluorspar had been floated in Canada in 1921 4 and a plant at Rosiclare had been floating fluorspar since March 1929, fluorspar flotation was given considerable impetus by the Mahoning developments, since some features of the separation were quickly adopted by other fluorspar companies. The Bureau of Mines5 reports that in the 10 years preceding 1938 only 50,552 tons of fluorspar flotation concentrates were produced in the United States. The rise from this almost nominal figure to 153,750 tons (largely acid grade) in one year (1944)6 is indicative of the activity in fluorspar flotation occasioned by the war. The industry thus proved to be in a position to expand and keep up reasonably well with the requirements imposed upon it by such developments as occurred in high octane aviation gasoline alkylation, in the use of Freon as a refrigerant and as carrier in the Aerosol "bug bomb," and in the atomic bomb project as well as in the expansion of other activities requiring hydrofluoric acid; such as, for example, the aluminum industry. Despite the fact that the greater portion of acid-grade fluorspar produced in the last few years went directly into war uses, the future of the acid-grade field still appears bright. As a result of the activity in fluorine chemistry during the war, it seems likely that in the relatively near future almost every phase of human endeavor will find some fluorine compound involved. The other three concentrates produced deserve some attention in these introductory remarks. The lead concentrates first produced contained both zinc and fluorspar but these did not interfere with their marketing. As will be pointed out later, the quality has steadily improved until today it is a relatively high-grade product. Although some zinc smelters accept concentrates containing limited quantities of fluorspar, it is a very objectionable impurity. Since flotation methods fail in the complete removal of the fluorspar, chemical methods were developed for

Jan 1, 1946

By R. S. Busk, E. G. Bobalek

THE relation between gases and metals has been a subject of increasingly active investigation during the past years, principally devoted to the study of metal-hydrogen systems. It has been found that hydrogen is soluble in most molten metals to an appreciable extent and somewhat soluble in most solid metals.1,2 In every known case there is a sudden decrease in solubility at the melting point. Thus a freezing mass of metal containing hydrogen in excess of the solid solubility must in some way expel that excess during the freezing process. This leads to internal blowholes, and such effects as pinhole porosity. Gas trapped in metal that is to be fabricated by a working process such as extrusion or rolling may be the cause of blisters. For some cases, notably in copper and iron alloys, the presence of hydrogen can lead to extreme embrittlement of the metal. The aluminum-casting industry has long recognized the importance of hydrogen in its techniques. Excess gas in molten aluminum alloys often leads to the formation of "pinhole porosity" in the solid casting.3 To prevent this hydrogen pickup it is necessary to avoid overheating the melt and to protect it from such sources of hydrogen as water. In spite of all precautions, it is sometimes necessary to extract hydrogen from the melt just before pouring by bubbling with a gas such as chlorine or nitrogen. Recently it has been found that somewhat similar effects are possible with magnesium alloys, in that the presence of hydrogen can induce or aggravate microporosity.4-6 This paper is primarily concerned with a presentation of some facts concerning the solubility of hydrogen in magnesium and its alloys, with some discussion of the significance of these facts in a practical sense. In any study of gas-metal systems it is important to bear in mind a clear distinction between adsorption on surfaces and absorption within the lattice.1 Considerable attention has been directed toward determining whether hydrogen is truly soluble in any solid metal, or whether the gas extracted from a sample was present at surfaces (external and internal) only.7 Most present day evidence supports the idea of true solution in addition to adsorption. A second important factor when dealing with gas solubility is the dependence of such solubility on external pressure. For diatomic gases such as H2, solubility in both liquid and solid metals apparently is proportional to the square root of the pressure, indicating a breakdown to a monatomic gas before diffusion into the lattice .2 For true equilibrium values of solubility, therefore, the pressure at the metal surface must be constant and, preferably, known. Very little has been published concerning the hydrogen-magnesium system. Winterhager has presented the most

Jan 1, 1946

By L. F. Mondolfo, F. A. Crossley

The mechanism of grain refinement by the addition of small amounts of titanium, molybdenum, zirconium, tungsten, and chromium to aluminum was investigated. The results indicate that the grain refinement is caused by the peritectic reaction which, by transforming the intermetallic compound into crystals of aluminum solid solution, seeds the melt with nuclei above the freezing point of aluminum. THE feasibility of reducing the grain size of aluminum alloy castings by the addition of small amounts of titanium, zirconium, molybdenum, tungsten, columbium, boron, and chromium has been known for a long time, and the use of some of these elements as grain refiners is common practice in the aluminum foundry industry. The purpose of the present investigation was to determine the mechanism by which these additions produce the grain refinement. Asato et al., on the basis of extensive work on copper, antimony, and silver alloys, presented a theory of grain refinement based on the occurrence of the peritectic reaction. Briefly, this theory states that during cooling of the melt crystals of the primary phase form, which react peritectically with the liquid upon further cooling. The peritectic reaction transforms at least partially the primary crystals into crystals of the secondary phase, which then act as nuclei for solidification of the remaining melt. As the peritectic reaction takes place the primary crys- tals break in pieces, and each piece acts as a nucleus. Fine dendritic crystals which can easily break are the most effective for grain refinement. Sicha and Boehm," in investigating the refining effect of titanium on an AI-Cu alloy, concluded that TiA1, crystals serve as nuclei to initiate crystallization, but did not offer further information on the mechanism of refinement. Bonsack in the discussion of their paper suggested that refinement was due to clouds of some solid in the melt, probably TiO² which hindered grain growth. Eborall,' after studying the effect of titanium, zirconium, vanadium, tungsten, columbium, chromium, and boron on some alloys, concluded that the peritectic reaction was not an essential feature of grain refinement. Her conclusion was based mainly upon the observation that under her experimental conditions (sand casting) the Al-Cr alloys, which undergo a peritectic reaction, did not show appreciable refinement. Cibula" investigated the mechanism of grain refinement and reported that two types of grain refinement exist: 1—Grain refinement produced by restriction of grain growth by the concentration gradient mechanism proposed by Northcott.' 2— Grain refinement produced by the presence of particles in the melt, upon which the melt crystallizes easily. He further concluded that very marked grain refinement results from a combination of the two mechanisms. Since Tic was found present in aluminum alloys refined by the addition of titanium, it was identified as the nucleating agent. In the case

Jan 1, 1952

By William C. Marshall, Frank G. Norris

The term "total operation" is meant to include problems that cannot be answered from the standpoint of either the blast furnace or the open hearth separately but must be studied by considering the interrelations of these two processes. There are other ways of expressing this idea, such as reference to the blast furnace and the open hearth as an integrated process or by emphasizing the interrelation and interaction of the two processes. Much progress has been made in metallurgy and other fields by breaking complicated processes and reactions into simpler parts and studying each of these intensively. This intensive study frequently is done under the controlled conditions of the laboratory experiment. The entire process is understood better by this specialized study of each of its parts. This procedure is so satisfactory that an understanding of unit operations is a fundamental requirement of chemical engineering. Much discussion of the open-hearth process is in terms of one heat or one furnace. By this is meant that the conclusions apply to one furnace, wherever it may be. Furnaces seldom occur singly; they are located in groups and these groups are located in steel plants having characteristic blast-furnace equipment. Problems that are affected by the number of furnaces operating, by the number of blast furnaces in the plant and by the fact that the open- hearth shop is dependent on the bla furnace capacity rather than on its o needs for the amount of iron available among those which, in contrast to "u operations," we have chosen to call "to operations." Many of these problems, such as cha ing delays and the general mechani problem of material handling, are familiar that merely to define " total op ations" brings them to mind. These pr lems are of such importance that alrea they have received careful thought 2 study and probably will merit furt study. As will be shown later, these mechan problems are so intimately related metallurgical problems of total operati that the effect of certain changes cannot ascribed with certainty to either a mech ical or a metallurgical cause entirely. Although the problems coming under general term of "railroading" are inclu in the problems of total operations, ' others are selected for the discussion of paper, One of these is strictly a problem composition; the other is strictly a prob of tonnage production. The problem of phosphorus is pres whenever basic open-hearth slag is used the blast-furnace burden. This practice not secured universal acceptance chi because of difference in preference for h manganese or low-manganese pig iron hjgh-manganese (2.00 per cent) iron is to made, open-hearth slag as a source manganese is usually cheaper than m

Jan 1, 1943

By Kenneth L. Cook

THE five serpentine masses exposed within the northern half of Riley County, Fig. 1, constitute a major part of the few exposures of igneous rock in Kansas.' Although not many subsurface data are available for this part of Riley County,2 six deep wellsV indicate that the basement complex lies between 2500 and 3000 ft below the earth's surface. A northwestward-trending ridge in the present basement surface, which extends across the northern half of Riley County, is indicated on Mettner's contour map.' The serpentine masses lie in a region that was active during Pennsylvanian and Permian time along two main tectonic trends, which may, in part at least, have developed contemporaneously." One trend is northeasterly, as evidenced by the Nemaha anticline, the Abilene anticline, the Voshell anticline, and many other smaller northeastward-trending folds. The other trend is northwesterly, as evidenced by the central Kansas uplift, the Salina basin syncline, and smaller northwestward-trending folds. The area of the Abilene anticline was actively deformed during much of this time, and the present surface rocks, for the most part Permian in age, show many normal faults." The Bala and Leonardville intrusions lie within a mile of the axis of the Abilene anticline, Fig. 1, as mapped by Wallace Lee;' the Randolph No. 1 and Randolph No. 2 intrusions lie within about 5 miles of the axis; and the Stockdale intrusion lies within about 8 miles of the axis. The igneous rocks have intruded horizontal or gently dipping limestones and shales that are late Permian in age.V he period of intrusion, according to Moore and Landes, was probably Cretaceous.' At present a detailed description of the petrography is available for only the Bala intrusion. Moore and Haynes' describe the rock at Bala as a green, serpentinized, porphyritic, peridotite breccia containing inclusions of shale. The ground mass consists chiefly of serpentine and calcite with considerable chromite (5 to 10 pct) and some magnetite. The phenocrysts consist principally of altered olivine with some altered augite and biotite. Although probably different in petrographic details, all the serpentine masses are somewhat similar in that 1) they consist of a dark green, fine-grained ground mass of igneous rock containing many xeno-liths composed of fragments of the neighboring sedimentary rock; 2) they tend to form small mounds on the landscape, thus indicating their greater resistance to weathering and erosion; and 3) they are magnetic. Previous Magnetic Survey of the Bala Intrusion: To the writer's knowledge, only the Bala intrusion had been surveyed with a magnetometer prior to the magnetic surveys discussed in this paper. Dreyer8 interprets the intrusion as a vertical, eastward-plunging dike, on the basis of the results of his magnetic survey, Fig. 1, with a vertical magnetom-

Jan 1, 1956

By Thomas Fraser, H. F. Yancey

PRIOR to the war just ended, Germany was the greatest coal producer in continental Europe. In 1943 the production of coal, bituminous and higher in rank, together with brown coal calculated to the equivalent amount of bituminous coal, is estimated to have been about 240 million metric tons, according to the War Department. Before the war production in Germany exceeded consumption. No other country in continental Europe except Poland had a large surplus. However, England's surplus was the largest in Europe as a whole. Before World War II the Ruhr Basin normally supplied about 70 pct of the total production of high-rank coal, the Saar and Aachen about 6 pct each, Upper Silesia about 14 pct, and Silesia and Saxony the remainder. Nearly one third of the brown coal was produced in the Rhineland, a little less than one half in central Germany west of the Elbe River, and about one fourth east of the Elbe. Bituminous coal and brown coal together constituted by far the most important energy resources of the old German Reich. Bituminous coal furnished nearly 70 pct of the total energy requirement, brown coal supplied about 25 pct, and water power, wood, petroleum and alcohol together aggregated only 7 pct. Because it was the most important single mineral resource of Germany, an excess of coal enabled the Reich to import nearly all the other mineral products that she lacked, such as iron ore from Lorraine. The area adjacent to the coal fields was supplied with gas from an interconnected grid. Similar electric grids are based on brown coal with the power stations at the mines. Coal tar provided the foundation for the development of the extensive German chemical industries as exemplified by the I. G. Farbenindustrie. For almost a century, German scientists have been adequately supported both by the State and by industry in studying improved methods of utilizing coal. In Germany the mineral rights were reserved by the State and ordered extraction of coal was enforced. Each lease comprised a relatively extensive area, which accounts for the generally large size of the mines and mining companies. In 1938 there were 160 mines in the Ruhr, with a total output of 125 million tons but go pct of the production was controlled by 20 companies. By far the largest single coal-mining company in Germany was the Gelsenkirchener Bergwerke A. G., which produced nearly 27 million tons in the Ruhr in 1937. Second was Saargruben A. G., a State-owned company operating in the Saar, which produced more than 13 million tons. Third was Bergwerksgesellschaft Hibernia A. G., with 10 million tons, also in the Ruhr. Briquettes are made from both bituminous coal and brown coal, but in 1938

Jan 1, 1946

By P. Nyul, S. Caplan, M. F. Lamorte, T. Gonda

Therrnal resistance is measured on GaAs laser diodes in the temperature range 77" to 300°K. These data show that typically the thermal resistance increases fifteen times from 77 to 300°K. The increase is attributed to the decrease in thermal conductivity of Gds. Nornzalized thermal-resistance experimental and calculated from published thermal-conductivity data) values are compared and good agreement shown. In many practical applications, it is desirable to obtain high average power output from laser diodes. Average power output is determined in large measure by the external efficiency and thermal resistance of the diode.'-3 The average input power with which a laser diode may be pumped is dependent on the thermal resistance. Thermal resistance has been studied over the temperature range from 77" to 300°K which is usually of interest in practical applications. This correspondence presents data on thermal resistance for GaAs laser diodes and compares them to values calculated from thermal-conductivity data. Junction heating arises from three distinct components: 1) joule heating, 2) nonradiative recombinations, and 3) reabsorption of radiation. In high-threshold lasers, joule heating predominates.4 Typically, the nonradiative recombination is not negligible and contributes significantly to junction heating. The loss caused by reabsorption may be of the order of the joule-heating loss.' The fabrication and the geometry of laser diodes have been described in other publications.5 The data presented were obtained from diodes which were fabricated from the same region of a wafer to minimize differences. Fig. 1 shows four types of heat sinks employed in this study. In types 1 and 2, the laser cavities are alloyed; pressure contacts are employed in types 3 and 4, and indium is plated on the inside faces to improve the intimacy of contact between the diode and the heat sink. The thermal resistance R is defined by the following relationship: where AT is the junction-temperature rise above the heat-sink temperature for the diode power dissipation Pd. For measurement of thermal resistance, a direct current is passed through the junction, in the range from 1 to 50 pct of threshold. The diode is placed in the laser mode by superimposing a current pulse of low-duty cycle on the direct current.3 Junction-temperature rise is obtained from the time-resolved laser spectrum at the leading edge of the current pulse.' Typically, the laser line shift is 2.5A per OK. The resolution employed in these experiments is 0.5A; therefore, the accuracy in the temperature measurement is 0.2K. Typically, the temperature rise is 2" to 20°K. The power dissipation is the difference between the dc power input, and the radiation power exiting the diode. The measurement accuracy is less than 1

Jan 1, 1968

By S. Floreen, H. W. Hayden

The effects of additions of iridium, rhodium, ruthenium, and platinum on the mechanical properties of Fe-C alloys were determined. Each alloying element significantly improved the toughness. The results support the general correlation that substitutional alloying elements that stabilize austenite are beneficial to toughness, but the reason for this improvement is not obvious at this time. The effects of substitutional alloying elements on the toughness of steel has long been a subject of both practical and theoretical interest. Despite the obvious importance of this subject, there has been little progress toward understanding the mechanisms by which alloying elements influence the fracture behavior. In some cases the deleterious effects of alloying elements have been shown to be due to mechanisms such as embrit-tlement of prior austenite grain boundaries or inhibition of cross slip in the ferrite lattice. In other cases, however, the reasons for the change in properties are not clear. This is particularly true for elements, such as nickel, that improve the resistance to brittle fracture. Several investigators'-3 have pointed out that there is a correlation between an alloying element's phase diagram with iron and its effect on toughness. Those substitutional alloying elements that stabilize austenite generally are beneficial to toughness, while ferrite-stabilizing elements generally are detrimental to toughness. The word "generally" should be emphasized, because exceptions to this rule can be found. Nevertheless, this correlation does offer a starting point at which to try to understand the effects of alloying elements on toughness. Thus far only two austenite-stabilizing elements, manganese and nickel, have been considered. In order to test the validity of this correlation several other austenite-stabilizing elements were evaluated. The noble metals, iridium, rhodium, ruthenium, and platinum, have binary phase diagrams with iron similar to the Fe-Ni and Fe-Mn diagrams. That is, each element expands the austenite field, and also higher concentrations of each element produce martensitic transformations at low temperatures. Presumably then, each of these elements should improve the toughness of steel. The present study was conducted to determine if this were so. EXPERIMENTAL PROCEDURE The alloys were made as l-lb air-induction melts using electrolytic iron and commercially pure noble metals. Each heat was initially deoxidized by a carbon boil, and further carbon was added to attempt to produce a 0.05 wt pct C content in each alloy. Before pouring, a final refining addition of 0.2 wt pct A1 and 0.1 wt pct Ti was made to each heat. The alloys were cast in a copper mold to produce ingots approximately 1 in. in diam and 5 in. long. The chemical compositions of the alloys tested are given in Table I. The residual nitrogen, aluminum, and titanium contents were all relatively constant at 0.003, 0.03, and 0.02 pct, respectively. The carbon

Jan 1, 1968

By H. L. Luo

SYSTEMATIC investigations of the Fe-Ga system have been reported only very recently."' The maximum solid solubility of gallium in a-Fe is nearly 50 at. pet at 900°C. However, from Ref. 1, it was not evident that the a-Fe solid solution could be retained successfully beyond 17.38 at. pet Ga by solid-state quenching. The present investigation reports the retention of a-Fe solid solution at 50 at. pet Ga by quenching from the liquid. An ordered phase of CsC1-type B2) structure was observed between 34 - 50 at. pet Ga. Since it was considered very probable that the CsCl structure would occur at high temperatures, alloy filings were also quenched by the conventional quenching technique. In addition to the CsCl phase, a second ordered phase of BiF3-type (DO3) structure was found in the range 25 - 30 at. pet Ga. Alloys were prepared from elements of 99.99 pet purity or better, induction-melted in alumina crucibles under hydrogen. After reweighing, the alloy ingots were cast into wires under argon. From the weight losses and the reproducibility of the lattice parameters, compositions were estimated to be within ± 0.3 at. pet. The techniques of quenching from the liquid state were reported before.3-5 Prior to quenching, a small section of cast alloy wire (30 - 50 mg) was melted in an alumina insert under an argon flow. The quenched specimens were in the form of flakes, typically 1 sq mm in area. For solid-state quenching, alloy filings passing 200 mesh were sealed under a reduced helium atmosphere in a thin-bottom silica tube. After heating for -30 min at the desired temperature in a vertical furnace, the sealed tube was rapidly dropped into ice water so that the thin bottom of the tube broke on impact. The quenched alloy filings were always ferromagnetic and could be collected by a magnet. X-ray diffraction patterns were taken with iron-filtered cobalt radiation in a 114.6-mm-diam Debye-Scherrer camera. High-angle lines were always resolved and spacings were computed relative to ? (CoKa1) = 1.78890Å. Lattice parameters were obtained from extrapolation against the Nelson-Riley function. The variation of lattice parameter with composition is shown in Fig. 1, together with the data of Dasarathy and Hume-Rothery.1 Uncertainties in the present measurements are within the dimensions of the symbols or indicated by error bars. X-ray diffraction lines indicative of CsC1-type ordering could be clearly identified for alloys of 34 - 50 at. pet Ga quenched from the liquid and alloys of 35 - 41 at. pet Ga quenched from -975°C. Within experimental error, no difference in

Jan 1, 1968

By E. C. Wright

THE following article is based on observation of college graduates entering the steel industry in technical work made during the past 25 years, the first five of which were spent as a college instructor in two engineering schools, and the last 20 in the employ of a large steel company that has hired hundreds of engineering graduates for steel-mill operations. The college graduates encountered during this period have come from many, colleges representing schools in Eastern States, Midwestern Universities, many Southern colleges, and many smaller colleges and normal training schools mostly in western Pennsylvania and Ohio. The college training of these students for engineering work naturally has varied widely and the educational qualifications of the entrants have been in many ways different. It was found at an early date that graduates of standard engineering colleges were much more adaptable than graduates in science from nontechnical schools. The engineering students seemed to be more suited to actual work in steel' plants and in general were better able to grasp a knowledge of the operations they observed. However, although the graduates of engineering schools have had somewhat better training -in physics, mathematics, and engineering, it has been a general and continual observation that most of the students employed have had inadequate training in the fundamental sciences. Since this discussion relates entirely to metallurgical engineers, it should be emphasized that students taking metallurgical engineering courses in college seem to be poorly trained in organic chemistry, physics, physical chemistry, thermodynamics, and any higher form of mathematics than simple calculus. It has been noted frequently that young engineers faced with problems in a mill that involve some mathematics generally flounder badly, and that they have little conception of physical chemistry. Another common deficiency lies in the young graduate's lack of knowledge of where to look for the more detailed literature on any subject. He reverts instinctively to some college textbook whose coverage is usually very elementary. It is recommended that such textbooks contain a bibliography of the source literature, and that students be taught to use theoriginal data. Many of the students had had previous courses in college dealing with metallurgical work such as steel melting, metallography, etc., but it was found that their grasp of these subjects was extremely sketchy. It was soon realized that an ordinary engineering graduate could be taught more about steel melting and manufacturing processes in a, few weeks in a. plant than he could learn in a college course on such subjects. A similar statement may be made regarding the ability of students to conduct laboratory work. Their lack of technique and skill in handling equipment and setting up experiments was soon apparent. It became neces-

Jan 1, 1946

By H. M. Dess, S. R. Bolin

A modifiedl Czochralski technique has been utilized to grow single crystals of YVO, pure or doped with europium or neodymium, from 1 to 2 in. long and 4 to 1/2 in. in dianz. An oxyhydrog-en gas-fired furftace zuas used in this ulork, and melts were contained in iridium crucibles. Successful application of the Czochralski ~vzethod was found to depend upon atmosphere control to prevent crusting and to limit melt decomposition, the establishment of symmetrical thermal gradients in the melt to obtain stable growth, and the selection of high-quality single-crystal seeds to prevent propagation of misorientations during growth and subsequent catastrophic cracking. The suitability of YVO4 as a host for laser-active trivalent rare earth ions has long been recognized. However, the problems associated with the growth of sufficiently large, good-quality single crystals have, until quite recently, seriously hindered satisfactory evaluation of the laser potentialities of this material. Both flux growth and Czochralski growth techniques were investigated at an early stage of interest in YVO,. The former method proved incapable of yielding crystals large enough for practical use,ly2 and the latter was beset with difficulties which took some considerable time to understand and overcome. Recently, however, the Czochralski growth process for YVO, has been improved along separate but similar lines of development by groups working independently in the Crystal Products Department of Union Carbide's Electronics Division and Bell Telephone Laboratories3 so that now good-quality single crystals of satisfactory size can be produced on a routine basis. Stimulated emission from a neodymium-doped YVO4 crystal grown by the Crystal Products Department of Union Carbide was obtained by O'connor4 of MIT, Lincoln Labs. An oxyhydrogen gas-fired furnace was used in this work, Fig. 1, and melts were contained in iridium crucibles. The starting material was 99.9 to 99.99 pct pure YVO4 powder purchased from the Chemical and Metallurgical Division of the Sylvania Electric Products Co. Typical impurity levels, determined by spectrographic analyses, were as follows: Si, 50 to 500 ppm Al, Fe, Mg, 5 to 50 ppm Ni, Pb, Mo, Mn, Ce, Cs, 1 to 10 ppm Initially, YV04 powders predoped with neodymium or europium were obtained from Sylvania. Later, however, because of a desire to grow a series of crystals containing relatively broad concentration ranges of these dopants, it proved more convenient to start with pure YV04 and mechanically admix Nd2O3 or Eu@~ powders plus equimolar amounts of V2O5. The empty crucibles were preheated to 1900" to 1950oC, a temperature range where melting occurred readily. The powdered YVO4 feedstock was then added incrementally. However, a marked tendency toward

Jan 1, 1968

By W. W. Smeltzer

The linear formation rates of wustite films have been determined over the temperature range 590° to 1030°C using a vacuum microbalance technique. These rates are dependent directly on the partial pressure of carbon dioxide, Activation energies for film and scale formation in carbon dioxide and oxygen atmospheres are equivalent to either the dissociation energies of carbon dioxide and oxygen, or the activation energy for the diffusion of cation vacancies in wustite. Of the metals, iron is the most widely used basic constituent of durable alloys despite its intrinsic property of converting at a relatively rapid rate to the oxides from which it is derived. This property has accounted partially for many investigations on the oxidation of iron at low and high temperatures. Interpretation of the results have been complicated by formation of multilayers containing the various oxide phases. To aid in elucidation of the oxidation kinetics, measurements have been carried out in this investigation on the growth of the wustite surface layer. There are several studies directly related to the objective of this investigation. The growth of multilayer scales has been demonstrated to be diffusion controlled in oxygen at atmospheric pressure over the temperature range 450" to 1200°C by Davies, Simnad, and Birchenall.' To gain an insight into the diffusion mechanism, Himmel, Mehl, and ~irchenall' determined the self-diffusion coefficients of iron in wustite, magnetite, and hematite. These results were used to evaluate the oxidation rates of iron and its oxides, taking as a basis the theoretical parabolic rate equation developed by Wagner., The evaluations were compared to experimental data and were shown to provide essential confirmation of this theory. Fischbeck, Neundeubel, and salzer4 have demonstrated that the oxidation of iron in carbon dioxide and other atmospheres at high temperature obeys a linear relationship. Because the Arrhenius temperature coefficients of the reaction rate constants changed at the A, point they concluded that the passage of iron into the oxide controlled the reaction. This viewpoint has been accepted by Benard and ~albot' to explain the occurrence of linear rates in oxygen before the onset of diffusion-controlled parabolic oxidation. This basic premise of a rate-controlling reaction at the iron/oxide interface has been questioned recently by Hauffe and Pfeiffer.' Since the formation of wustite may follow a linear or parabolic relationship depending on the pressure of the gaseous re-actant, they propose that linear oxidation is determined by a chemisorption reaction while parabolic oxidation is controlled by diffusion. As confirmation of this viewpoint, Hauffe and pfeiffer6 and Pfeiffer and ~aubmeyer' have established that the linear scaling constants of wustite formation at 1000°C in carbon-dioxide or low-pressure oxygen atmospheres

Jan 1, 1961

By M. J. Marcinkowski, D. Koskimaki, A. S. Sastri

THIS is the second in a trilogy of investigations carried out in order to understand the solid state transformations and their accompanying effects on the deformation behavior of near-equiatomic Ni-Ti alloys. The first stage of this effort has dealt with the strictly martensitic structures obtainable in these alloys, i.e., those in which diffusion processes were not involved.1,2 These martensites could be produced either by rapid quenching or by plastic deformation of the originally B2 type phase. The present investigation, on the other hand, will deal with those transformations in Ni-Ti which do involve diffusion. A majority of investigators3-10 have shown that the B2 modification of TiNi, which is stable at elevated temperatures, decomposes into one or both of the intermetallic compounds NiTi2 and Ni3Ti below about 650°C. On the other hand, this has been disputed by several Workers was undertaken in order to resolve this discrepancy, as well as to shed more light on the nonmar-tensitic decomposition of B2 NiTi. EXPERIMENTAL PROCEDURE Sample preparation, fabrication, and examination were the same as those described previously in Ref. 2. In addition to the 50 at. pct Ni (55.06 wt pct) hypoeu-tectoid alloy used previously, a second hypereutectoid alloy containing 54.4 at. pct Ni (60 wt pct) was also prepared for this study. RESULTS AND DISCUSSION The equilibrium diagram for the Ni-Ti alloy system in the vicinity of Ni-Ti is shown in Fig. 1. The solid lines have been established by the work of Poole and ~ume-Ftothery4 whereas the dotted lines are based on findings obtained in the present investigation as described below. Structure and Morphology. Fig. 2(a) shows a bright field transmission electron micrograph of a two-phase structure obtained in a polycrystalline Ni-Ti alloy that was furnace cooled (approx 200°C per hr) from 1050' to about 300°C. Large plate-shaped precipitates can be observed in a matrix which was found by electron diffraction to possess the high temperature B2 structure. A selected area diffraction pattern of the region covered by Fig. 2(a) is shown in Fig. 2(b), while Fig. 2(c) is a detailed schematic interpretation of Fig. 2(b). The B2 matrix reflections are illustrated by squares while those of the precipitate are shown as circles. The d values associated with the precipitate reflections could be determined quite accurately since the reflections from the B2 matrix, for which the lattice constant is known precisely, were simultaneously present in the diffraction patterns. All of the reflections

Jan 1, 1970

By William F. Cerini, Willis R. Battles, P. H. Jones

A test for determining the plugging characteristics of an oil-well injection water has been developed. It consists in measuring changes of the filter rate of a water at constant pressure with cumulative throughput when passing the water through a medium grade sintered glass disk. Application of the test method was made to the water used in the Union Oil Company's experimental water flood of the Chapman zone in the Richfield field, Orange County, Callfornia. This water developed increasing plugging tendencies upon aging, even though the finished water from the plant filter exhibited few such characteristics. The plugging material was found to consist of calcium carbonate, ferric hydroxide, and organic substances that were presumed to be bacterial. Various method of stabilizing this water to prevent the formation of plugging material were attempted. Lowering the pH to approximately 6.4 by injecting carbon dioxide provided a moderately satisfactory means for stabilization but a better method of stabilizing this water was found to be first aging and then filtering. Introduction An experimental water-flood project was started on the Chapman zone of the Richfield field in March 1944 and has been described in a previous paper.' It consists of a single injection well drilled between old producing wells. A water-treating plant using primary alum flocculation, sedimentation and chlorination followed by secondary flocculation, sedimentation and fltration is employed to process the water before in@ion. In all of the water-treating operations, the system is open to the air, and no attempt is made to prevent the loss of carbon dioxide or absorption of oxygen by the water. The clear water is stored in a covered concrete basin and pumped through a Transite line to the suction of a high-pressure pump at the injection well' The high-pressure tubing in the well to the injection zone is cement lined. The untreated injection water is a mixture produced with the oil from the Chapman and Kraemer zones and is supplied from the disposal system. Because the injection well was relatively deep (injection zone about 3400 ft.) and would be expensive to replace, it was believed imperative to supply a nonplug-ging injection water and to develop laboratory procedures for evaluating the treated injection water with respect to its formation plugging properties. This report describes the development and application of the test procedure based on the assumption that the plugging properties could be determined by measuring the progressive decrease in flow rate of the water through a porous medium. If the quality of the injection water was good enough so that the plugging action on the porous medium was of small magnitude, it was reasoned that the tendency to impair flow in the formation would not be serious.

Jan 1, 1946