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By S. T. Wlodek, John Wulff

Dense, adherent, and ductile coatings of chromium can be applied to Molybdenum by selectively freezing out the chromium solute from a supersaturated copper-or tin-rich liquid alloy. The successful exploitation of this technique depends on the control of variables common to any freezing process. Under the most favorable combimtion of supersaturation, nucleation, and mass-transfey, coatings as thick as 0.004 in. can be obtained. In exploratory experiments it was found that a coating of chromium may be applied to molybdenum by immersing the molybdenum body in a supercooled copper-chromium or tin-chromium melt and selectively freezing out the contained chromium onto the molybdenum body. Supercooling of the liquid metal plating bath can be achieved by cooling, or the maintenance of thermal or concentration gradients in the melt. The technique is similar to conventional dip-plating procedures where the sample is immersed in a molten bath of the pure plating medium, except that in these studies, the plating medium consisted of a dilute solution of chromium in liquid tin or copper. The success of this method requires that the base material to be plated be isomorphous with the coating and insoluble in the plating bath. In addition, the plating bath, while having an appreciable solubility for the coating component, must have negligible solid solubility in the solid plate. Such relationships exist in the molybdenum-chromium, chromium-tin, and chromium-copper systems. Liquid tin and copper are satisfactory as the plating solvent, because although chromium is appreciably soluble in both of these liquid metals, solid inter-solubility is almost negligible, and no compound formation occurs. The same relationships exist between molybdenum and copper or tin except that the solubility of molybdenum in liquid tin or copper is insignificant. It is this combination of solubility relationships, as well as the completely isomorphous nature of the molybdenum-chromium system, which allows the formation of a chromium coating on molybdenum by the selective freezing mechanism. Since the main deterrent to the widespread use of molybdenum for high-temperature structural applications is its poor oxidation resistance, the formation of a dense and ductile chromium coating on molybdenum may well be of commercial significance. In addition, the basic principle of coating formation by selective freezing should be applicable to other metallic or even nonmetallic systems. The precipitation of the solute from a liquid metallic solution, for the formation of a protective coating, has not been previously considered in the literature. Frequently, however, a similar phenomenon has been described in the corrosion of metallic heat exchangers by liquid metals1 wherein temperature gradients in the liquid metal heat-transfer medium result in the formation of layers or deposits of metallic residue2 in the cooler portions of the system. Impregnating techniques using liquid baths have been tried as a plating process. Semchyshen and Barr, for instance, have successfully diffused chromium into molybdenum by immersing the molybdenum specimen in a liquid tin-chromium or copper-chromium alloy. This simple holding technique fails to produce a layer of pure chromium and requires prolonged immersion to allow for the diffusion-activated enrichment of the molybdenum. During the course of this investigation, most of the phase relations published for the copper-chromium4 and molybdenum-chromium4 systems, were found reliable. It was necessary, however, to investigate the solubilities of chromium and molybdenum in liquid tin as well as the solubility of molybdenum in liquid copper. These determinations were made by a simpie weight loss technique on materials of the same purity as used in the plating studies. The results of these solubility studies are given in Tables I and I1 and indicate that although the solubility of molybdenum in liquid

Jan 1, 1961

By Robert L. Gower, John H. Cash

Interconnections for integrated circuits operating at rnicrowaue frequencies rzust be formed as microwave transmission lines. This paper describes the fabrication of one type of microwave transmission line known as microstrip, which can be fabricated on momlithic integvated circuits by deposition of 0.1- to 2.0-mil-thick metal and dielectric films. A microstrip line consists of a narrow conducting strip separated from a gvound plane by a dielectric material. Thick films of good conducting materials are required for low loss at high frequencies. Vacuum-evaporation methods for depositing aluminum and silver films are described. The narrow conducting strip forming the top conductor is defined by photoresist-etching techniques after the thick rnetal film is deposited. Gold plating with a photoresist-masking technique is also used to forrrz thick metal conductors. The microstrip dielectric layer is formed by deposition of suitable dielectric films 0.1 to 2.0 mils thick. Several deposition techniques were investigated. Electron-beam evaporation of quartz is described. Electrical characteristics of deposited microstrip lines at microwave frequencies are included and the microwave power attenuation as a function of conductor and dielectric thickness is given. It is concluded that the deposition of microstrip transmission lines is a practical way to achieve low-loss interconnections in monolithic integrated circuits. CONNECTIONS between devices in low-frequency and digital circuits are usually made by connecting the devices with a length of conductor such as a metal lead oi- a wire. If this method were applied to microwave integrated circuits, the reactance of the connection due to the series inductance and parasitic capacitance would be very high, in fact too high to permit successful circuit operation. In addition, resonance and antenna effects would occur at high frequencies, especially when the connections approach the wavelength.' Connections which are sections of transmis- sion line will overcome these difficulties. The electromagnetic field is confined to the volume of the transmission line, parasitic effects are not present, and circuit design utilizes familiar transmission-line techniques. TRANSMISSION LINES One type of transmission line geometrically adaptable to integrated circuits is known as micrstri. A microstrip line can be generated from a coaxial line as shown in Fig. l(a). The outer conductor of the coaxial line is distorted into an ellipse (b) and finally separated at the extremities of the ellipse to form the strip transmission line shown in (c). One of the ground planes is then removed, leaving a conducting ground plane and a narrow conducting strip separated by a dielectric. Two configurations of the microstrip line were considered in this investigation, Fig. 2. Type (a) is fabricated from a semiconductor slice with the ground plane and top conductor deposited on each side of the slice. The semiconductor slice serves as the die lec-

Jan 1, 1967

As desirable as it may be to a geologist to have maximum detail in any geological report, the task of doing so for an area as vast as British Columbia within six average size magazine pages is clearly impossible. As a result, it has been necessary to draw a fairly broad picture of the geology on the following pages, but it is one which should be adequate to give the reader a concept of what rock is where in the Province. In preparing this horseback ride over the strata of the Province, much reliance has been placed on various reports appearing in trade and Canadian Government journals. Of these, one in particular stands out. Entitled "The Cordilleran Region", this report has been authored in three parts by H. S. Bostock, R. Mulligan and R. J. W. Douglas, respectively, and is included as a major chapter of the book Geology and Economic Minerals of Canada. Published in 1957 by the Department of Mines and Technical Surveys, the book has provided the extensive quotes, taken from each of the three authors, which appear on the following pages.

Jan 12, 1963

By Francis L. Sperry

Up to within a few years, the consumption of nickel has been more directly dependent upon the available supply than that of any of the other useful metals. The Gap mine, in Lancaster county, Pennsylvania,* has been, for the last quarter of a century, the only property in this country furnishing nickel in paying quantities. Its yearly output was about 300,000 pounds of metallic nickel, or nearly half the amount used annually in the United States. Foreign nickel from mines on the New Caledonia islands, in the South Pacific, found entrance into our markets as the production of the Gap mine fell off. The price of nickel was constantly maintained, and no special effort was made to extend its use. Over-production was cautiously guarded against, and all surplus metal was held by the banking-houses of the Rothschilds, who assumed the bonded indebtedness of the Sociètè le Nickel. The opening of the Ontario nickel-mines has, however, brought about a radical change; and nickel from the Sudbury district can be delivered in New York within four days, and in European markets within two weeks, as against two months consumed in transporting South Pacific ores. Former prices have been irretrievably smashed, and European trade-journals comment favorably on the influence which Canadian nickel has had in making lower prices, and breaking the backbone of the " nickel trust." Production and Costs. The quantity of nickel produced and the prices which it commanded may be briefly summarized as follows: The total production of the world from 1840 to 1860 was about 100 to 250 tons yearly of metallic nickel; from 1860 to

Jan 1, 1896

By John A. Church

In the year 1874, when the price of pig-iron was still high, that staple product became the subject of discussion in the newspapers and among those philosophers who are determined to know the "reason why" for all things. The object of the inquiry was to find out Why iron did not fall in price as much as some other things had fallen. Indeed, there seemed to be an impression that iron and gold ought to move on nearly parallel lines, for the fact was constantly brought forward that iron then cost twice as much as it did before the war, though gold had returned to within twelve or fifteen per cent. of its former value. After some time the papers, by what seemed to be nearly unanimous consent, reached the conclusion that the maintenance of high prices was the work of the furnace proprietors, who, as the result of their shrewdness, were pocketing enormous profits. No proof was given to support this opinion, and the figures of cost and sale that were produced were of the most general kind, and used in the most vague manner. Visiting the president of the Thomas Iron Company, whose great works at Hokendaqua and Catasauqua, in Pennsylvania, are so well known as the largest and among the best conducted in America, I found him quite willing to meet the vague suspicions of the newspaper wiseacres, by a publication of the figures contained in the furnace-books of his company. These were accordingly given to the world through the Engineering and Mining Journal, and attracted the general attention they so well deserve. Though my own name became connected with these statistics, from the fact that I used them as the basis for the first attempt ever made to calcalate the furnace economy of an American works, I can, without the suspicion of egotism, say that the statistics referred to are the most valuable contribution the literature of American blast-furnace work has yet received, for their interest is independent of personal considerations, and due entirely to the fact that they represent faithfully the details of practice in one of the most prominent American works. They are an exact transcript of the furnace-books, and form a body of accurate information of the greatest value to the metullurgical student. Their importance is shown by the fact that though the theoretical conclusions which I based upon them have been several times attacked, not one of my critics has made the slightest contribution to

By John A. Church

IN the year 1874, when the price of pig-iron was still high, that staple product became the subject of discussion in the newspapers and among those philosophers who are determined to know the "reason why" for all things. The object of the inquiry was to find out why iron did not fall in price as much as some other things had fallen. Indeed, there seemed to be an impression that iron and gold ought to move on nearly parallel lines, for the fact was constantly brought forward that iron then cost twice as much as it did before the war, though gold had returned to within twelve or fifteen per cent. of its former value. After some time the papers, by what seemed to be nearly unanimous consent, reached the conclusion that the maintenance of high prices was the work of the furnace proprietors, who, as the result of their shrewdness, were pocketing enormous profits. No proof was given to support this opinion, and the figures of cost and sale that were produced were of the most general kind, and used in the most vague manner. Visiting the president of the Thomas Iron Company, whose great works at Hokendaqua and Catasauqua, in Pennsylvania, are so well known as the largest and among the best conducted in America, I found him quite willing to meet the vague suspicions of the newspaper wiseacres, by a publication of the figures contained in the furnace-books of his company. These were accordingly given to the world through the Engineering and Mining Journal, and attracted the general attention they so well deserve. Though my own name became connected with these statistics, from the fact that I used them as the basis for the first attempt ever made to calculate the furnace economy of an American works, I can, without the suspicion of egotism, say that the statistics referred to are the most valuable contribution the literature of American blast-furnace work has yet received, for their interest is independent of personal considerations, and due entirely to the fact that they represent faithfully the details of practice in one of the most prominent American works. They are an exact transcript of the furnace-books, and form a body of accurate information of the greatest value to the metallurgical student. Their importance is shown by the fact that though the theoretical conclusions which I based upon them have been several times attacked, not one of my critics has made the slightest contribution to

Jan 1, 1876

By Thomas A. Simpson, Russell A. Walker

Hydrogeological techniques were used to solve problems of slope stability in open-pit mines of the Eufaula bauxite district, Ala. Geologic and hydrologic data were evaluated and used to design a system of dewatering wells to enable the operators to mine bauxite more efficiently and economically. Walls of open-pit mines in the district were subsequently stabilized by the operation of the dewatering system. Three open- pit mines, each at varying stages of the mining process, of the A.P. Green Refractories Co., were used to develop a sequential series of guidelines that indicate how to effectively remove ground water from the formations surrounding the ore bodies in the district. The use of sound engineering principles in well design, in combination with the correct interpretation of the pit hydrology provided the basis for solutions of the slope-stabilization problem and aided in the economical removal of bauxite from mines of the district.

Jan 1, 1976

Discussion of the paper of DAVID COLE, presented at the New York meeting, February, 1915, and printed in Bulletin No. 9S, February, 191.5, pp. 431 to 444. R. H. RICHARDS, Boston, Mass.-The Butchart riffle seems to violate, according to our preconceived notions, some of the very essential principles of the Wilfley riffle, and therefore ought not to succeed, but it does. On this account it must conform to other very important principles, or it would not succeed. It would beinteresting to know what these principles are which enable it to succeed. E. P. MATHEWSON, Butte, Mont.-I cannot, explain the principles on which this riffle acts, because I have not given it personal attention. All I can say is that I first saw the riffle in operation several years ago at the Steptoe Valley mill in Nevada, and I was told that a man had been around there guaranteeing that these riffles would make the table do twice as much work and do it better than with the ordinary Wilfley riffles. I heard nothing further about it for a long time. I heard about a year ago, from David Cole, the author of this paper, that the riffles were a success, and that he was using them at Morenci, and if, we were interested he would send the inventor to show us how they worked. As we knew of David Cole's reputation, we invited Mr. Butchart to come up and show us how his riffles worked. We did not have sufficient confidence in the invention to guarantee Mr. Butchart his traveling expenses, but lie came up entirely at his own expense and put in a set of the riffles on one table. It was known as a roughing table in our No.

Jan 5, 1915

By John W. Burd

A system is described for the simultaneous deposition of epitaxial layers on as many as eight substrates. A high degree of uniformity of both physical and electrical characteristics is achieved in the films. Variation of film thicknesses is consistently less than ±10pct within a wafer and from wafer to wafer within a run with the variation typically on the order of 55 pct. Composition variation of GaAs1-x PX layers within a wafer and from wafer to wafer within a run is consistently less than 51 pct. Electrical evaluation of the films by several techniques indicates excellent doping uniformity within a wafer and from wafer to wafer within a run. Mobilities for lightly doped GaAs films at 300°K are consistently >6000 cm2 v-1 sec-1 and mobilities > 7000 cm2 v- 1 sec-1 are regularly attainable. Techniques for the preparation of material with carrier concentrations from 1 x 1015cm-3 to 1 x 1019 cm-3 n-type and 5 x 1016 to 5 x 1018 cm-3 p-type are discussed. METHODS for the preparation of 111-V compounds by vapor phase reactions have been extensively reported in the literature.1-6 Almost all of the apparatus described for these various methods are suitable for processing one or at the most a very limited number of wafers simultaneously. With the recent rapid advances in the use of vapor grown GaAs for microwave oscillators and GaAs1-xPx as visible light emitters the requirements for these materials are steadily increasing. In order to satisfy these requirements it is necessary to move from a laboratory scale apparatus to one which is capable of processing a large number of wafers simultaneously. Desirable features would be a high degree of uniformity among the wafers and good reproducibility from run to run. The apparatus to be described fulfills these requirements very well. DISCUSSION The various methods reported in the literature can be classified under three headings: 1) closed tube, 2) open tube, and 3) the close-spaced method. Of these three the open-tube method is the most amenable for scale-up to a manufacturing process. It is the most versatile and the various operating conditions can be more precisely controlled than with the other two methods. A number of chemical reactions may be used to achieve vapor-phase growth of 111-V compounds. Sev-era1 of the more generally used reactions are shown in Fig. 1. All of these reactions have the following points in common: 1) generation of a volatile group III(Ga) species by the reaction of the transport agent (halide or HC1) with either Ga or GaAs, 2) introduction of the Group V(As and/or PI component, 3) a method of adding dopant, if desired, and 4) a region in which deposition from the vapor will occur and form as a single crystal epitaxial film on the substrates. The laboratory scale reactors permit the hot re-actant gases to flow into the relatively cooler deposition zone and pass successively over the several substrates which are arrayed along the long axis of the tube parallel to the gas flow. With this arrangement the composition of the reactant stream is continually changing as solid material is deposited on each successive substrate. As a result of this changing gas composition the reaction driving force also changes from substrate to substrate and the degree of uniformity of layer thickness, doping level, and so forth, is poor. This effect can be partially overcome by imposing a controlled temperature gradient along the deposition region to compensate for change in gas composition. However, even when this is done variations in layer thickness on the order of 30 to 40 pct are common and as high as 50 pct are frequently experienced between adjacent wafers in the tube. To expand this arrangement to a large number of wafers would only increase the nonuniformity from the first to last wafer in the line. From the above discussion the two undesirable features of changing gas composition and temperature gradient become evident. A reactor system which eliminates or minimizes these undesirable features is one in which the apparatus is mounted vertically as shown schematically in Fig. 2. The vertical mounting permits the disposition of a number of substrates on a suitable support so that all wafers are at the same vertical height in the furnace and hence at essentially the same temperature. By using only a single row of wafers the reactant gas mixture passes over only one substrate in its path through the reactor. Thus the two undesirable features of changing gas composition and temperature gradient are minimized. An additional design feature which further minimizes temperature variations is rotation of the substrate holder. Rotation serves to integrate any radial temperature gradient existing around the resistance heated furnace. A photograph of a reactor assembly at the completion of a run is shown in Fig. 3. MATERIAL PREPARATION Apparatus. Although any of the several chemical systems shown in Fig. 1 are adaptable for use in this apparatus the one generally used is System 2, the hydride synthesis system. This system has been de-

Jan 1, 1970

By AIME AIME

THE annual session for the election of officers and transaction of other official business of the Institute, which must be held, in accordance with the By-Laws, in New York on the third Tuesday in February, was the only session scheduled for the morning of Feb. 19. Many members gathered in the auditorium at 10 o'clock, and President George Otis Smith presided. He said that his report was best set forth in the reports of the other officers and committees, which were avail-able in printed form. Productive activity had characterized the Institute's year and a number of new ventures had been successful. He felt that he had "rattled around" in the office of president, as he had traveled some 39,000 miles during the year in visiting the various Sections, having visited everyone that had held a meeting during his term of office. He spoke of the educational effect on a president of these broad contacts and suggested that a three-year course would be even more enlightening than one.

Jan 1, 1929

By J. Chipman, N. J. Grant, J. H. Walsh, T. B. King

WITH the development of adequate sampling and analysis techniques, much information has been obtained concerning the behavior of hydrogen in the steel bath during the course of steelmak-ing operations. From studies of this type it has become clear that the slag has an important role to play in determining the hydrogen content found in commercial products. A knowledge of the behavior of hydrogen in slags is necessary to round out our knowledge of hydrogen in steelmaking practice; with this information we are better able to assess practical methods of control. In this paper a method developed for analyzing slags for hydrogen content, studies of the solubility of hydrogen in synthetic slags, and studies of the variation of hydrogen content in slag and steel in industrial heats will be described. Previous Work—While very little has been done in the past to determine the hydrogen content of metallurgical slags, measurements have been made on such slag-like materials as geologic magmas and glasses. Goranson as made extensive studies of the solubility of water in natural and synthetic granites. Many workers have investigated the solubility of gases in synthetic and commercial glasses, but the recent work of Russell" is the most extensive. Russell found that the solubility of water in glass was proportional to the square root of the water vapor pressure in water vapor-oxygen mixtures. It was found that the solubility could either increase or decrease with temperature depending on the glass composition. Wentrup, Fucke, and Rief,' and Piper, Hagedorn, and Backes' have extracted hydrogen by holding a slag at 1300" and 800°C respectively in vacuum. Wentrup et al. reported hydrogen and water vapor as evolved together while Piper et al. passed the evolved gases from the hot extraction treatment over hot ferromanganese to reduce the evolved water vapor to hydrogen and, therefore, reported the analyses in terms of total dissolved hydrogen. Yavoiskii has reported hydrogen and nitrogen analyses on steelmaking slags. Dobrokhotov, Povol-skii, and Khan have studied the hydrogen content of basic open hearth steel under slags of varying viscosity. These authors reported that the hydrogen content of the steel bath increased as the fluidity of the slag was increased by the addition of bauxite. They recommended that a viscous slag be used and the steel tapped without deoxidation in the furnace to ensure a low final hydrogen content. Analysis of Slags for Hydrogen Development of Apparatus—The vacuum fusion analysis equipment described by Shields, Chipman, and Grant" was modified for the analysis of slags." This method depends upon the reduction of water in the slag to hydrogen, which is readily determined by the method used for hydrogen in steel. Preliminary experiments were made with a eu-tectic ferrosilicon melt as the reducing agent. Other experiments included the use of graphite and molybdenum crucibles. The ferrosilicon alloy bath was found to produce a thick coating on the furnace tube which could adsorb hydrogen. Graphite produced CO by the reduction of FeO, MnO, and SiO2 in such quantities that analysis for hydrogen was virtually impossible. Molybdenum, while giving a low blank value, could reduce the slag sufficiently to produce a volatile oxide which again was found to adsorb hydrogen. The arrangement finally adopted is shown in Fig. 1. The molybdenum sheet served as the induction-heated susceptor, and was separated from the escaping gases by alumina guide tubes. An outer jacket of alumina protected the quartz furnace tube, and alumina and quartz stools completed the assembly. The falling sample is shown wrapped in aluminum foil, 0.002 in. thickness, which acted as the reducing agent' This foil was careful'~ washed in acetone and an d and then dried in hot air before wrapping the weighed slag sample for charging into the apparatus. Investigation of the hydrogen content of the aluminum foil itself showed that a small quantity of hydrogen was released in vacuum, but had no relation to the weight of the aluminum charged. This quantity of hydrogen was

Jan 1, 1957

By B. G. Ricketts, A. Kelly, P. A. Beck

The isothermal kinetics (at 200" to 400°C) of subgrain growth and of softening were studied in a 99.997 pct pure Al crystal rolled to 80 pct RA, under conditions where recrystallization did not take place. It was found that the kinetics of subgrain growth and of softening were similar, and that the correlation between subgrain growth and softening was in first approximation independent of the annealing temperature. It has been shown by Heidenreich' by means of electron transmission microscopy and by Hirsch and Kellar2 by means of an X-ray microbeam technique that the crystals of heavily cold-worked polycrystalline aluminum consist of subgrains of approximately 2µ diam, which are slightly disoriented with respect to each other. This substructure is found on cold working at room temperature, without annealing. A preliminary study has been previously published3 of the softening upon annealing at 350°C of a heavily cold-rolled aluminum single crystal. Softening and X-ray line sharpening for such a rolled aluminum crystal were later studied in more detail as a function of annealing time and temperature.4 Perryman5, 6 has studied the recovery of polycrystalline aluminum after cold rolling. By means of phase contrast microscopy he found that the subgrain size increases with the annealing temperature but does not alter very much with annealing time at a given temperature. In the present work further study was made of softening as a function of annealing time and temperature and subgrain sizes were determined by two different techniques in an attempt to find any correlation that may exist between softening and subgrain growth. Subgrain size measurements were made both by the X-ray microbeam technique and by transmission electron microscopy. EXPERIMENTAL PROCEDURE For the X-ray studies specimens were cut from

Jan 1, 1960

By S. Feuerstein, L. Rice

The effect of low pressures on the flow and fracture behavior of molybdenum is described. For poly crystalline samples, room-temperature tensile tests indicate greater ductility under 10 Torr than under intermediate pressures up to and including atmospheric pressure (760 Torr). In addition, tests conducted at 760 Torr under atmospheres of air, dry nitrogen, and purified argon exhibited no apparent difference in mechanical properties. Critical tests involving baking in situ as well as those involving single-crystal deformation further imply that the ductility effect is a pressure-dependent phenomenon related only to the fracture process. This dependency is discussed in terms of adsorption and diffusion contributions. THE effect of very low pressures on material properties has heretofore been presumed to be important only for substances possessing relatively high vapor pressures at ambient temperatures. Research has therefore been concentrated primarily on organic solids and liquids, and in some instances on metals such as zinc and cadmium. Most vacuum-effect studies' on the mechanical behavior of metals have been performed under conditions of either cyclic loading or creep rupture at elevated temperatures, i.e., over extended time periods. These studies were not restricted to high vapor pressure materials but also encompassed such metals as gold, copper, and nickel. Very little concern, however, was placed upon the importance of a vacuum environment on the mechanical behavior of metals subjected to a simple unidirectional deformation at ambient temperatures. A tension test is generally of short duration as compared to a creep test, and at room temperature vacuum effects if any would be expected to be surface-limited. In early 1963, Kramer and podlaseck2 reported a change in the bulk flow behavior of aluminum single crystals during room-temperature tension tests. The deformations were performed under pressure conditions of 760 to 3.4 X 10-8 Torr and indicated for the first time a vacuum surface effect contributing to the bulk tensile behavior of metal specimens. As a consequence, an experimental program was initiated in this Laboratory to study the effects of ultrahigh-vacuum conditions on the mechanical behavior of metals. The results of a preliminary study on poly-crystalline molybdenum3 revealed, unlike Kramer's observations of changes in the stress-strain behavior, only an increased ductility under ultrahigh vacuum. Flow behaviors were nearly identical for all tests re- gardless of pressure. This paper presents comprehensive results obtained in this area of research. 1) EXPERIMENTAL PROCEDURE Three material categories were used in this study: sintered and are-cast polycrystalline molybdenum of nominal purity 99.93+ pct and single-pass electron-beam zone-refined molybdenum single crystals having a nominal purity level of 99.99+ pct. The interstitial levels (weight percent) as determined by the Materials Testing Laboratories, Division of Magnaflux Corp., were as follows: sintered molybdenum (C— 0.005, H—0.0004, O—0.015, N—0.008); and arc-cast molybdenum (C-0.0038, H-0.0003, O-0.015, N-0.023). Single-crystal molybdenum obtained from Materials Research Corp. had a typical interstitial analysis of C-0.0015, H-0.00007, O—0.00045, and N-0.0001. Tensile specimens having a 5 mm diam by 50.8 mm length were prepared from these materials. An average grain diameter of 0.059 mm was obtained for the sintered specimens following a 4-hr, 1600°C heat treatment. Grain sizes from 0.019 to 0.149 mm were obtained in the arc-cast specimens following heat treatments from 1100° to 1600°C for 1 hr. This series of specimens was used exclusively for the grain-size effect studies. All samples were electrolytically polished in 97 pct sulfuric acid solution prior to testing. Experiments were performed at room temperature in an ion-pumped ultrahigh-vacuum system positioned in an Instron tensile machine, Fig. 1. A constant strain rate of 4.2 x 10-4 sec-1 as derived from crosshead displacement was assumed for the deformations. Starting vacuums ranged from 2 to 0.5 X 10-10 Torr. These pressure measurements were made using corrected values4 of an NRC Redhead gage. Comparative readings were also made against a G.E. triggered dis-

Jan 1, 1967

By Robert B. Hall, Charles W. Bauer

Alunite, KA13(SO4)2(OH)6, was used from the 15th century until early in the present century as a source of potash alum and aluminum sulfate. Since early in this century its use for this purpose has declined to virtually nil with acid treatment of bauxite or clay replacing alunite as a source of alum. During the First World War alunite served as an emergency source of potassium sulfate fertilizer in the United States and Australia. More recently, alunite has been investigated as a nonbauxite ore of aluminum, with potassium sulfate and sulfuric acid as recoverable byproducts. The Soviet Union established a commercial-scale plant in the mid-1960s producing cell-grade alumina from alunitic ore and recovering byproduct potassium sulfate and sulfuric acid. Interest in nonbauxite ores, including alunite, is expected to continue in countries that presently are dependent on imports of bauxite or alumina to support their aluminum industries. The US has the largest aluminum producing and fabricating industry in the world but imports more than 90% of its aluminum-bearing raw materials. This chapter reviews the status of alunite as a potential source of aluminum with byproduct fertilizer, and the resources available to support this industry, whenever this becomes economically feasible. Historical Background Alunite has received little attention until recently, yet for centuries it held a higher place than many of the industrial minerals considered essential today. The deposits of alunite at Tolfa, northwest of Rome, were mined almost continuously from 1462 until about the middle of the present century (DeLaunay, 1907; Lombardi, 1977). The potash alum made from the alunite, called Roman alum, was a valued commodity in international trade, being used in the making of paper, in tanning leather, and as a mordant in textile dyeing. The industry at Tolfa is said to have been controlled by the Vatican and was a source of revenue for the Papal State until fairly recent times (Lombardi et al., 1977). Since early in the present century, the preferred method for making alum has been by acid treatment of bauxite, clay, or other aluminous material, so that alunite has fallen into near-total disuse as a source of alum chemicals. Appreciable quantities of mixed alunite-kaolin rock still are quarried in the Tolfa district for use by the Italian cement industry (Lombardi and Mattias, 1979), but the role of this material in the making of Italian cement is not clear. A large deposit of alunite-bearing rock in Chekiang province, mainland China, is said to have yielded a "great quantity" of alum over a period of several centuries (Yih, 1931). During the 19th century, alunite deposits in France, Spain, Australia, and other countries were exploited as raw material for making potash alum and aluminum sulfate. Interest in alunite was revived during the First World War, not for alum, but as an emergency source of potassium sulfate fertilizer. Large veins of nearly pure alunite had just been discovered on Alunite Ridge, 11 km southwest of Marysvale in Piute County, Utah (Butler and Gale, 1912), and these were quickly brought into production for making potash fertilizer to replace supplies cut off from the famous deposits at Stassfurt, Germany. An estimated 225 kt of Marysvale alunite was mined and processed at that time (Callaghan, 1973). Similarly, Australian alunite deposits were mined as a source of potash fertilizer during both world wars (Hall, 1978).

Jan 1, 1983

By John C. Calhoun, F. W. Gooch, J. P. Everett

The results of two sets of displacement experiments are reported. In the first set of experiments various solutions of sugar in water were displaced by other solutions of sugar in water. In the second set oils were displaced by water. Each set of experiments was performed on a linear system made of cemented silica sand grains. These displacement tests were made to evaluate the behavior when the ratio of fluid viscosities between the displacing and displaced phases was varied. A further consequence of the test results is a comparison between displacement behavior when the displaced and displacing phases are miscible as with sugar solutions and when they are immiscible as with oil and water. INTRODUCTION Buckley and Leverett1 have presented a theory for the displacement of oil by gas or water based upon the relative permeability concept. This theory presents the displacement of oil as occurring in two phases, an initial or primary phase preceding the breakthrough of the displacing phase and a subordinate or secondary phase during which both oil and the displacing phase flow simultaneously through the same porous section. These authors gave the results of calculations to show that the percentage of oil displaced during the primary phase by water drive would be dependent upon the ratio of the viscosity of the oil to that of the water. No experimental evidence was reported by these authors to substantiate their theory. Qualitatively, however, it has been found to be in agreement with many observed field results. Laboratory investigators have been in general agreement in reporting for air or gas drive2,3 a small primary phase of production and a large secondary phase. Reported investigations on water drive3,4,5 have shown instances where both primary

Jan 1, 1950

By William Y. Holland, Roger M. Cook

In view of the increasingly widespread deterioration of concrete structures as the result of the interaction of the alkalies sodium and potassium released by hydration of portland cement and susceptible rocks and minerals in aggregates, it is believed that a paper summarizing the geographic distribution of these aggregates will be of interest to producers and users of concrete, concrete products, and concrete-making materials. THIS paper reviews the problem of alkali-aggre-gate reaction in concrete and describes the geologic and geographic occurrence and distribution of alkali-reactive sand and gravel in western United States. It includes no discussion of crushed stone or synthetic aggregates. Most deposits of sand and gravel are accumulations of particles of rocks and minerals from a variety of sources, and it is not unusual for at least one or two varieties of the rocks to contain some form of reactive material. Examination by petro-graphic methods of many sands and gravels, as well as manufactured aggregates, has shown that a comparatively high proportion of the deposits does contain, in greater or lesser degree, rocks and minerals known to be deleteriously reactive with the alkalies of cement. Fortunately the amount of reactive materials is commonly less than that necessary to cause deleterious effects in concrete. As investigation of unsound concrete structures progresses, it becomes evident that the alkali-aggre-gate reaction is even more widespread than supposed, Figs. 1 and 2. Even though some parts of the country appear at present to be immune, further investigations will probably show that the effects of alkali-aggregate reaction can be seen in many structures in these areas, although only on a small scale in most of them. Many concrete structures will, of course, have lived their useful life before disintegration from this cause is serious, and in others the alkali-aggregate reaction may never become significant even though the microscopic evidence of reaction is present. The alkali-aggregate reaction first was reported to be a cause of deterioration of concrete in 1940 when Stanton1 described expansion of concrete pavements in California. Similar expansion and deterioration of concrete was recognized during succeeding years in concrete structures located in many parts of the country, but particularly in the western states. A number of concrete laboratories2 became interested in the problem. It was soon determined that only certain combinations of aggregate and cement caused the alkali-aggregate reaction to take place, and moreover that the reaction progresses only in the presence of water. Further research proved that cements containing more than 0.60 pct total alkalies (pct Na,O + 0.658 x pct K2O), when used with aggregates containing appreciable amounts of reactive ingredients, caused the reaction to take place, usually with subsequent deterioration of the concrete. During the last few years this limitation has been adhered to in both government and private construction as the maximum allowable alkali content of cement to be used with aggregates of known alkali reactivity. Because of this limitation, it appears that deleterious reaction either has been reduced or eliminated in many recently built structures in which it probably would otherwise have occurred. Recent tests have shown that the degree of expansion obtained with any particular cement-aggre-gate combination depends not only on the alkali content of the cement but also upon the relation of this alkali content to the amount and degree of reactivity of reactive constituents in the aggregate.' In laboratory mortar bars, opal and cements with alkali content of as low as 0.2 pct (as equivalent of Na2O) have produced deleterious expansion as the result of alkali-aggregate reaction. These experiments demonstrate that aggregates containing even 0.1 pct of opal are deleteriously reactive. It was soon determined that alkali-silica gels were formed by the interaction of the alkalies of the cement and the reactive aggregate, Figs. 3 and 4. Osmotic or swelling pressures produced by the continued hydration of these gels cause expansion of the concrete with resulting cracking, warping, and dislocation. Evidence of the alkali-aggregate reaction can be seen by a petrographic study of the deteriorated concrete. Among the first structures studied by this method was Parker Dam on the Colorado River, California-Arizona. In the concrete from this dam pebbles of rhyolite, andesite, siliceous limestone, and chalcedonic chert were found to be reactive.

Jan 1, 1954

By D. M. Schuster, E. Scala

The elastic effects occurring in the matrix of a composite reinforced by discontinuous fibers were studied by means of photoelastic techniques. A hirefringent plastic was employed as the matrix material with high-strength a Al2O3 whiskers as the reinforcing fibers. It was found that for whiskers aligned parallel to the tensile load direction: (I) Matrix reinforcement occurred along the length of the whisker to within about 5 diameters of the whisker tip for a length to diameter ratio, L/D, of 40. (2) Significant stress concentrations were created in regions immediately surrounding the tips; the fine as-formed tapered ends exhibited the minimum stress concentration whereas the square-ended whisker produced relatively high values, K r 2.5 for L/D = 40. (3) The axial and radial stress distributions could he determined quantitatively; the stress distribution at the whisker-matrix interface was in general agreement with theoretical calculations. (4) The highest source of stress concentration occurred at points of fracture in whiskers which had ruptured after incorporation into the composite. Whiskers aligned perpendicular to the load direction neither reinforced nor caused appreciahle stress concentrations in the matrix. ThE properties of composites have generally been formulated empirically on the basis of macroscopic tests. There are still many questions concerning the mechanical and chemical interactions occurring at the interface between the reinforcing fiber and its matrix. Continuously reinforced plastics and dispersion-hardened metals represent the two extremes of composite reinforcement. Whether artificially produced or formed in situ, the whisker composite falls between these two extremes and is an example of discontinuous fiber reinforcement. The effect of fiber shape, size, surface condition, and end configuration on the stress distribution in the matrix is important since the presence of stress concentrations, especially in any high-strength, thin-wall structure, could become the cause of catastrophic failure. DOW,' in his theoretical discussion of discontinuous fiber reinforcement, has pointed out that appreciable stress concentrations occur at the tips or ends of the reinforcing fibers. It is the purpose of this study to examine directly, by means of the photoelastic technique, the stresses which occur in the vicinity of a discontinuity or whisker tip and to measure qualitatively and quantitatively the effects of whisker geometry when embedded in a birefringent matrix material. The use of sapphire (a A1,O3) whiskers was decided upon as the reinforcing agent because of their high elastic modulus (E- 60 X 106 psi) and in some cases strengths in excess of one and a half million psi. Sapphire whiskers are of further practical interest since they retain large fractions of their strength up to temperatures approaching the melting point (3720oF).2 The whiskers were grown, by the vapor-phase reaction commonly employed,3 as part of this study to insure a physically uniform supply. Tensile and bend tests were performed to verify that the whiskers were of the expected ultra-high strength. The high-strength whiskers can be identified and selected from the combustion boats by surface perfection, shape, and size; otherwise, strength values can vary by a factor of ten or more. Macroscopic defects are quite common on the surface of large bladed whiskers and the principal experiments were conducted with hexagonal whiskers of about 0.002 in. diameter and lengths ranging from 0.1 to 0.4 in. Upon completion of these two phases of the experiment, several birefringent resins were evaluated. A plastic, developed by Zandman,4 which is supplied by the Budd Co., was found most suitable and was used as the matrix material for the whisker composite throughout the study. It has a sensitivity of 60.5 lb per in. order, calibrated in tension and cures without introducing residual stresses. Young's modulus for this matrix material is 430,000 psi in the fully cured condition. Since good wetting and bonding between the sapphire and the matrix material is essential to the interpretation of the results, a wettability test was performed. The contact angle was measured to be 168 deg where perfect wetting is defined as 180 deg; therefore, the Budd Plastic wets the sapphire

Jan 1, 1964

By Rodney P. Smith

The rate of motion of the boundary between a single-phase a-iron region and a two phase a-iron plus ?-iron, or a-iron plus cementite region has been measured on decarburization at several temperatures between 500" and 865°C. These data, together with data for the carbon content of a-iron at the boundary, yield the diffusivity of carbon in a-iron. The activation energy for carbon diffusion is 19.8 kcal per mole for the temperature range —50° to 150°C and increases to an average value of 23.0 kcaL per mole for the temperature range 727" to 865°C. AS part of an investigation of the diffusivity of carbon in iron using a steady-state method,' the diffusivity of carbon in a-iron was determined at the temperatures 802" and 851°C. The diffusion constant thus obtained was larger, by nearly a factor of two, than that predicted from the combined results of stanley2 and of Wert.3 It seemed desirable, therefore, to continue the investigation. Since the temperature range in which the steady-state method can be conveniently used is limited, we have chosen a decarburization method, based on the laws of diffusion in metal accompanied by a phase change.4,5 If the initial carbon content of the Fe-C alloy is such that two phases coexist at the decar-burizing temperature* and decarburization is car- ried out such that the surface is maintained at substantially zero wt pct. C, the carbon distribution after a time, t, will be as shown in Fig. 1. The boundary between the single-phase and two-phase regions moves from y = 0 to y = x in the time, t, where x is proportional4 to tl". If the initial carbon (content of the sample is Ci, and CB is

Jan 1, 1962

By H. M. Chance

By courtesy of the officials of the Chicago, Burlington and Quincy railroad, I am permitted to publish the results of an examination made in 1887 and 1888 of' the country west of the Black Hills, and lying between the Black Hills and the foot-hills of the Big Horn Mountains in the northeastern part of Wyoming. With the exception of the country constituting the foot-hills, or the encircling ridge or rim of the Black Hills proper, all of this area is occupied by rocks of Cretaceous age. In the central part of the Black Hills are found the tin-bearing granites, the mica-schists, and gold-bearing slates, already so well known. Surrounding this central area of older rocks (which should be considered as the "Hills" proper) are the attenuated representatives of the Palzeozoic, dipping gently away from the Hills in every direction, overlaid by the gypsum-bearing Mesozoic, which here forms a bold high ridge or rim, completely encircling the Black Hills, and known as the inner ridge. Overlying, and apparently conformable to this, we find the Dakota sandstone, which likewise forms a prominent ridge or rim, known as the first or outer ridge. This is the formation which contains the coal now worked at the mines near Newcastle. It is also the formation in which the best oil-wells have been obtained in the "Stoakdale," or "Beaver," and the " Belle Fourche " oil-districts. Overlying it are the Colorado shales, forming the great plains drained by Beaver creek and the south fork of the Cheyenne river, and extending west to the Belle Fourche, near Donkey creek, where the overlying Fox Hill formation (thin) and the Laramie group, the great lignite-formation, are first seen. The Laramie group occupies the surface from the Belle Fourche at Donkey creek west to the foothills of the Big Horn mountains at Buffalo, an air-line distance of some seventy or eighty miles.

Jan 1, 1891

By F. H. Rhines

Page Foreword. By F. N. Rhines............................525 Design Factors for the Metal Forms with Which Powder Metallurgy May Compete. By Fred P. Peters...................... ......527 Discussion..................................530 Powder Metallargy as Applied to Machine Parts. By A. J. LanghamMer........531 Discussion......................... . Pole Pieces for Electric Motors from Iron Powder. By F. V. Lenel...........535 Discussion....................... . Bearings from Metal Powders. By W. R. Toeplitz.................542 Discussion.........................'.........549 Brushes and Allied Powder-metal Parts. By R. R. Hoffman . .............'550 Electrical Contacts Manufactured from Metal Powders. By E. I. Larsen........554 Sintered Magnets. By C. B. Fulton........................557 Friction Articles from Metal Powders. By C. T. Cox..................565 Discussion..................................567 Certain Characteristics of Silver-base Powder Metallurgical Products. By I?. R. Hensel and E. I. Larsen........................ ....569 Discussion............................... . . . . 579 Some Properties of Sintered and Hot-pressed Copper-tin Powder Compacts. By C. G. Goetzel..................................580 Discussion..................................593 The Sintering of Metal Powders—Copper. By C. J. Bier and J. F. O'Keefe......596 Some Experiments on the Effect of Pressure on Metal-powder Compacts. By Jerome F. Kuzmick..................................612 Discussion.................................. 630

Jan 1, 1945