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By Harry K. Ihrig

The hot-working of iron and steel is an art dating back to antiquity, but until about 25 years ago, relatively few alloying elements were used, and these were present only in small percentages. With the exception of sulphur, the amounts of other elements in steels did not markedly affect their hot-workability. The references in the literature on the effect of other elements on the hot-workability of steel are usually reports of failure of these steels in forging or rolling.1-8 With the increased use of alloying elements, and their use in larger amounts, it was observed that many of the new steels were red short in certain critical ranges or at all hot-working temperatures. The stainless steels are particularly difficult to hot-work. The determining of the correct conditions for piercing, rolling and forging of these alloys by experimentation in the mill often results in large losses of these expensive metals. It also is found that the hot-workability limits of many types vary from heat to heat, and hence poor results are obtained on changing to a new heat after a previous one has rolled satisfactorily. To determine the effect on hot-workability of iron to which various elements have been added, it was necessary to devise a method that could be used on small quantities of metal. In such a method, the minimum number of variables should be present, and the procedure should be simple, quick and correlatable with large-scale hot-working operations. Sauveur,9 in the first Henry Marion Howe lecture in 1924, described the effect of carbon on the ductility of steels in torsion near their critical points. He found that carbon increases the plasticity of gamma iron. In the 1930 Campbell Memorial lecture,10 he gives the effect of carbon, chromium, and chromium and nickel on the ductility of steels under 2000°F. in torsion. Ellis11 has studied the malleability of steels at various elevated temperatures by means of a single-blow drop-hammer test. In this test the percentage decrease in height of standard cylinders is taken as a measure of their malleability. He has shown that in the low-alloy steels studied, carbon has a greater effect than nickel, chromium and vanadium. In 1938 the first tests were run on a new quantitative hot-workability test in the laboratories of the Globe Steel Tubes CO. Thum12 mentioned it in 1940. An illustration of the apparatus was published in January 1942.'' The effect of a few alloying elements on the hot-workability of metals was shown in a description of the test in 1944.14 Description of Test Method The method adopted after a trial of several others is a rapid twisting of bars to failure in a furnace. The standard-size bar was chosen as 9/16 in. It is prepared from larger pieces by forging and cold-

Jan 1, 1947

By E. R. Parker, R. H. Thielemann

The conventional short-time tensile test provides a reliable means of predicting the sustained load-carrying capacity of steels only when the temperature is such that continuous plastic flow does not occur. At elevated temperatures, stresses considerably less than the short-time rupture value may produce continuous flow, with fracture occurring only after long periods of time. The amount of flow or creep accompanying failure varies for different steels, and depends, to a large extent, on the temperature and the duration of the test. Service records of cracking stills, steam superheaters and high-temperature boilers have shown that brittle fractures sometimes occur with little or no warning. In installations of this type, localized stresses are often encountered, and steels must be capable of withstanding a certain amount of deformation without fracture. The sustained-load rupture test determines the expected life and corresponding ductility of steels at various stresses and temperatures. It also yields additional information regarding the effect of micro-structure and metallurgical stability on the high-temperature properties. Present Status of Sustained-load Rupture Test The sustained-load rupture test conducted at elevated temperatures is not entirely new. Dr. Zay Jeffriesl presented in 1919 the results of a large number of rupture tests made on copper, iron and tungsten. These tests were made with various strain rates and at temperatures ranging from the boiling point of liquid air to 1000° C. At that time he observed the interesting phenomenon characteristic of metals, that a temperature exists below which a metal is ductile and breaks with a transcrystalline fracture (through the grain) and above which the metal is brittle and breaks with an intergranular fracture (through the grain boundaries). He observed that this temperature varied with the testing speed, and that a minimum temperature, slightly above the recrystallization temperature, existed at which the cohesion of the grains themselves was

Jan 1, 1939

By R. H. Thielemann, E. R. Parker

The conventional short-time tensile test provides a reliable means of predicting the sustained load-carrying capacity of steels only when the temperature is such that continuous plastic flow does not occur. At elevated temperatures, stresses considerably less than the short-time rupture value may produce continuous flow, with fracture occurring only after long periods of time. The amount of flow or creep accompanying failure varies for different steels, and depends, to a large extent, on the temperature and the duration of the test. Service records of cracking stills, steam superheaters and high-temperature boilers have shown that brittle fractures sometimes occur with little or no warning. In installations of this type, localized stresses are often encountered, and steels must be capable of withstanding a certain amount of deformation without fracture. The sustained-load rupture test determines the expected life and corresponding ductility of steels at various stresses and temperatures. It also yields additional information regarding the effect of micro-structure and metallurgical stability on the high-temperature properties. Present Status of Sustained-load Rupture Test The sustained-load rupture test conducted at elevated temperatures is not entirely new. Dr. Zay Jeffriesl presented in 1919 the results of a large number of rupture tests made on copper, iron and tungsten. These tests were made with various strain rates and at temperatures ranging from the boiling point of liquid air to 1000° C. At that time he observed the interesting phenomenon characteristic of metals, that a temperature exists below which a metal is ductile and breaks with a transcrystalline fracture (through the grain) and above which the metal is brittle and breaks with an intergranular fracture (through the grain boundaries). He observed that this temperature varied with the testing speed, and that a minimum temperature, slightly above the recrystallization temperature, existed at which the cohesion of the grains themselves was

Jan 1, 1939

By A. M. Gsudin, F. W. Bloecher, C. S. Chan-s, P. L. De Bruyn

M ANY elements can now be obtained in radioactive form. The radioisotopes have the same chemical properties as the corresponding inactive forms, differing from them only by their nuclear instability. This combination of properties permits radioelements to act as atomic tracers, the tracer atoms revealing themselves at the time of their decay with emission of electrons and positrons (beta radiation), helium nuclei (alpha radiation), or electromagnetic radiation (gamma radiation). The tracer technique is particularly attractive for the study of surface chemistry problems in general and flotation problems in particular because of its extreme sensitivity. A large proportion of the ionizing events, initiated by the characteristic decay emissions in a radioactive sample, can be recorded by radiation probes of suitable design and geometry. An idea of this sensitivity can be gathered from the following example: assume that 0.001 mg of pure RaD (radiolead), a beta-ray emitter, is used in a flota¬tion tracer experiment. This is 1210 X 10-1 mole; since the fraction trans¬formed per second (the so-called decay constant), is 9.92 X 10-10, the number of ionizing events per second would be (6.023 X 1023 X y,,, X 10-1) X 9.92 X 10-10 = 2.845 X 106. (The decay constant is expressed in sec-'. Its product with the half life, expressed in seconds, is the pure number, natural logarithm of 2 = 0.693. The half life is the length of time required for decay of one half of the total number of radioactive atoms of one particular type.) (See reference (1) at the end of this article.)

Jan 1, 1948

By Willis H. Carrier

PARTICULAR interest in the ventilation of deep mines, especially those in South Africa, has been created by a very complete system of cooling of the world's deepest mine, the Turf shaft of the Robinson Deep in Johannesburg. The writer visited this mine in January, 1936, and again in 1937. During these visits and subsequently, a considerable part of the theory involved in rock cooling in tunnels was developed and this has been checked by practical observations of the rates of rock cooling made within mines. The purpose of this paper is to set forth the method of attack of the mine problem. The cooling or air conditioning of mines by the use of mechanical refrigeration was not wholly new 1-5 when the Robinson Deep installation was made. The first mine to be cooled was the Morro Velho mine, in Brazil. The first installation in this mine was put into operation in December 1920, the refrigerant being ammonia.5 The surface cooling gave considerable benefit but it proved inadequate as greater depths were reached, therefore in 1929 two centrifugal refrigerating machines were installed at the 6000-ft. level. These were used in conjunction with the surface cooling system to furnish additional cooling at the lower levels. This later installation used Carrene as a refrigerant. This nonflammable refrigerant, having a boiling point of 104º at sea level, insured reasonable safety, since all parts of the machine operated at subatmospheric pressure. Very favorable reports have been received on the effectiveness of this installation, but no recent data are available. An interesting feature of that plant is that the condenser water is cooled by spraying it into the exhaust air from the mine at the base of the ventilation upcast, which permits the water to be cooled within a few degrees of the wet-bulb temperature of the air entering the upcast, and the only water that has to be supplied for condensing purposes is that lost by evaporation, or about 0.5 per cent of the volume circulating through the condenser. This plan affords an ideal means for the removal of the heat load from the refrigerating system, and of course also from the mine itself. In many mines, however, especially those in South Africa, there is no

Jan 1, 1938

By R. Schuhmann Jr., P. J. Ensio

As a first step in a study of the physical chemistry of copper-smelting slags, experimental measurements were made of the oxygen pressure of simple iron-silicate slags in equilibrium with solid iron. The experiments consisted in bubbling CO2-CO mixtures through the slags in iron crucibles and in finding the equilibrium ratios of CO2 to CO. From the data, activities and partial molal heats of solution FeO and SiO2 in the slags were calculated. THE ternary system FeO-Fe,O,-SiO, is the simplest system which can represent adequately the important chemical properties of the slags formed in matte smelting and converting. Accordingly, the experimental study of slags in this system was started as the first step in a general research program on the thermodynamics of copper smelting. A recent paper by one of the authors' outlines this general research program and shows in some detail how information on thermodynamic properties of iron-silicate slags, especially information on oxygen activities, is essential to a full understanding of the chemistry of copper smelting. The FeO-Fe,O,-SiO, system also is the basis of slags produced in other processes, such as acid steelmak-ing processes, and is important in relation to the behavior of silicious refractories. In addition, data on the physicochemical properties of iron-silicate slags should contribute to a general understanding of the nature of slags, since at present such data for all kinds of slags are relatively meager. The principal quantitative information already available on iron-silicate slags consists in Bowen and Schairer's constitution diagram for slags in equilibrium with metallic iron,' Darken and Gurry's complete and precise thermodynamic study of the Fe-0 system,",' and Darken's study of the phase equilibria in the Fe-Si-o system. From the results of this previous work, it was clear that a complete thermodynamic study of ternary iron-silicate melts was a major undertaking which would have to be broken down into parts, including the working out of the ternary equilibrium diagram as well as extensive activity measurements on slags. The experimental measurement of oxygen activity, using CO-CO, and other gas mixtures as yardsticks of oxygen activity, was the basis of Darken and Gurry's study of the Fe-0 system. From the experimental measurements of oxygen activities over a large range of temperatures and compositions, they were able to calculate the activities of other species such as Fe, FeO, Fe,O,, etc., and also the other important thermodynamic properties in the Fe-0 system. At the start of the present investigation, it appeared that the same approach would be fruitful for the study of iron-silicate melts. Also, the experimental measurement of oxygen activities seemed particularly attractive because oxygen activity itself is a quantitative measure of oxidizing or reducing power, which is an important variable in copper-smelting slags. The slag compositions in equilibrium with yFe appeared most suitable for the first investigation of this kind, for the following reasons: 1—Good constitution data2 were available. 2—An iron crucible could be used, thus affording a simple solution to the refractory problem without introducing contarnination. 3—With Fe activity fixed, at unity with respect to a standard state of solid Fe, measurements of 0 activity could be followed by simple calculations of activities of FeO and other Fe-0 complexes and of SiO,. 4—This starting point afforded several possibilities for cross-checking with previous work,

Jan 1, 1952

By AIME AIME

EARLE EDWARD SCHUMACHER, the new Chairman of the Institute of Metal, Division. is well known to the metallurgical profession. His election a, Chairman is the culmination of fifteen years' service to the Institute, beginning in 1930 when he was elected Member. Since that time he has served as member of the I.M.D. Data Sheet Committee. 1935-40; Papers and Publication Committee. 1936; Executive Committee. 1937-1910: Papers and Programs Committee, 1937-1938. (Vice-Chairman, 1939-40, Chairman. 1941-12): Annual Award Committee. 194142. (Vice-Chairman, 19431: Vice-Chairman, LM.D., 1943-44; Chairman Publication Committee, 1943-44; member Powder Metallurgy Committee), 1944. Pew other men have contributed so Much time anti effort in so many way- to the interests of the metals branch o4 the A.I.M.E.

Jan 1, 1945

By P. Shahinian, H. H. Smith, M. R. Achter

Crack growth rates are measured at elevated temperature in a resonant fatigue machine from vibration frequency decreases calibrated in terms of crack depth. Crack growth rates in Type 316 stainless steel at 500º and 800°C show a sharp increase with oxygen pressure in an intermediate pressure range and little or no change at high and low pressures. At 500°c, I torr of oxygen reduces the fatigue life by almost a factor of 100 in comparison to that in vacuum and raises the growth rate of shallow cracks by the same At At 800°C the effects are smaller. Changes in slope in the crack growth rate curves are discussed in terms of a model in which rates of surface production and of surface coverage by gas are compared. The use of a calculation method in which the surface exposure time is equal to X/v, where x is the interatomic spacing and v is the growth rate, makes it possible to obtain order of magnitude agreement at 500°C between the observed pressure and the predicted pressure at these slope changes. At 800°C oxidation becomes a .factor and the data cannot be treated by simple adsorption theory. THE decrease in the fatigue life of metals as a function of gas pressure usually follows a stepped curve with virtually all of the decrease concentrated in a sharp drop in a transition zone at intermediate pressures and little or no change at low and high ranges. A number of models, differing in the details of the mechanism, have been offered to explain the shape of the curve. Measurements of crack growth in aluminum as a function of gas pressure by Bradshaw and Wheeler' and Hordon2 demonstrated opportunities for quantitative comparison to evaluate the proposed models. Since comparable data were lacking at high temperatures, in the present work rates of crack propagation were measured in Type 316 stainless steel at 500" and 800°C as a function of oxygen pressure. Choice of this material was dictated by two considerations; it is stiff enough at these elevated temperatures to resonate with the regenerative drive on our fatigue machine and it is known to display a large effect of environment. A new method of calculation is described to predict the gas pressure at the critical point. EXPERIMENTAL PROCEDURE Because of the difficulty of measuring crack depths directly at high temperatures, an indirect method was developed based on the decrease in the resonant frequency with the growth of a crack. A reversed bending, constant amplitude fatigue machine, described previously,3 vibrates a specimen at its resonant frequency, automatically records any changes in it and shuts itself off after it has reached a preset value of frequency decrease. The record of frequency change is used to determine the rate of crack growth. Sheet type specimens of Type 316 stainless steel, Fig. 1, incorporated a sharp, shallow notch to localize the formation of a single crack. After machining, they were annealed in a vacuum of l0-6 torr either at 1066" (lot A) or 871°C (lot B) and then electropolished in an acetic-chromic acid solution. Bending strains were measured at 500" and 800°C by an optical technique4 and reported as total strain without correction for the notch. At 500°C, the 0.141 pct strain was 0.085 pct elastic and the remainder plastic. At 800°C the 0.062 pct strain was all elastic. To convert frequency decrease to crack length, calibration curves were obtained by interrupting the vibration at stated intervals of frequency decrease. The crack depth was measured microscopically at a magnification of X400 and reported as the average of the measurement on each edge. Some specimens were sectioned for crack measurement while others were returned to the machine and fatigued further. There was good agreement between the two methods. Before beginning the vibration, the vacuum chamber was first evacuated cold to 1 x 1O-6 torr, then heated to the operating temperature and held there until the pressure was again reduced to 1 x10-6 torr at which time oxygen was introduced to the desired pressure. In this investigation the vibration frequency was nominally 10 cps and a decrease of 0.6 cps was taken as the failure point. The choice of the frequency decrease to represent failure has no appreciable effect on the fatigue life because the crack is growing very fast at this point.

Jan 1, 1970

By AIME AIME

BY the end of 1943, the United States will be able to produce aluminum at a rate of 1,150,000 tons a year. How much aluminum is 1,150,000 tons? It is sufficient to replace every railroad passenger car in this country three times a year. Or, it would put a thirty-piece aluminum cooking utensil set in every one of America's 34,000,000 homes with enough metal left over to make 5,000,000 miles of aluminum transmission cable, such as was used in the electrification of much of rural America. Expansion of aluminum production capacity for the war program has occurred in three steps: (1) expansion by private industry; (2) the letting of contracts by the Defense Plant Corp. for the construction of additional aluminum plants which may remain after the war to compete with existing facilities; and (3) the more recently announced D.P.C. program for the building of emergency plants to make aluminum, using stand-by power available in large metropolitan centers power of relatively higher cost, making it questionable whether such plants, now gravely needed, will be able to compete in a peacetime economy.

Jan 1, 1943

By C. Schlumberger, M. Schlumberger

The object of this paper is to clarify the idea, so important when exploring by potential methods, of the depth of investigation attainable by electrical measurements. After defining, with some precision, .the term "depth of investigation'' in geophysics, the authors show how it is possible to regulate this depth in potential methods and to obtain an 'electrical drilling" from surface observations. They consider also the difficulties encountered in deep measurements and indicate how it is possible to reach greater depths than those having an industrial interest. Depth of Investigation The term, depth of investigation, in its general sense, is easily understood. For instance, a driller who can pull cores from a depth of 2000 m. is capable of working, with accuracy, to that depth. By means of a properly placed drill, he may locate an orebody at a depth of 1999 m., however small this orebody may be. On the contrary, the term as used in geophysics requires precise elaboration. As a matter of fact, no geophysical method, irrespective of the physical property studied (density, magnetic permeability, conductivity), can discover a very small body at a great depth because, in practice, the physical parameter upon which such a geophysical method is based is never regular enough, throughout the ground, to distinguish the feeble anomaly caused by the small, deep-lying body from the numerous anomalies due to irregularities of the encasing terrains. Aside from this question of the ratio between the size of the body being hunted for and its depth of burial, a second factor plays its role in the possible depth of investigation; that is the difference, for the parameter under consideration, between the body and its surrounding material. The greater this difference, and the more homogeneous the encasing terrains, the greater is the possible depth of investigation. This being generally established for all geophysical methods, it is possible to distinguish two main classes of these methods, from this same point of view

Jan 1, 1932

By M. C. Lavine, H. C. Gatos, R. S. Mroczkowski

The structure of GaAs-Ge heterojunctions prepared by a back-melting process was studied by X-rav diffraction, melallographic, and electron-micro-analyzer techniques. The boundary region between the GaAs and the germanium was found to consist of a four-layered band. A discontinuity between the two inner bands was brought about by solidification occurring simultaneously from the GaAs and the germanium side. The junction material OH either side of the central discotinuity was found to have grown as a single Crystal with the orientation of the parent substrate. It was found essential to determine the GaAs-Ge phase diagram. This was accomplished by a series of alloys containing 0 to 40 wt pet GaAs. Over this range the diagram is a simple eutectic with the eutectic point at 74 wt pet Ge and 845 C. The limiting- solubility of Coils in germanium was found to bc less than 5 wt pet. The Kossel divergent-beam X-ray technique was used to study orientation relationships across the boundary lager. A great deal of effort has been recently expended on the electrical properties of heterojunctions. Little attention, however, has been given to the metallurgical variables which may be of importance in the formation of the junctions. The present work was undertaken to investigate some of the more pertinent metallurgical aspects of interface-alloyed GaAs-Ge heterojunctions. Such parameters as solidification processes, composition gradients, orientation effects, and the accommodation of crystal structures have been the objects of study in this program. EXPERIMENTAL PROCEDURES Phase Diagram. The phase diagram of the GaAs-Ge pseudobinary system was determined by means of cooling curves. A Bridgeman furnace was employed with the center section maintained at 1200°C and the upper section at 800°C. Melts varying from 0 to 40 at. pct in GaAs content were used. Each charge was incapsulated under a two-thirds atmosphere of argon in a carbon-coated quartz tube. Five min in the furnace hot zone provided rapid melting and homogenization. The capsule was then removed to the cooler portion of the furnace. Cooling times were of the order of 3 min. The resulting homogeneous microstructure indicated that equilibrium conditions were obtained by this procedure. Formation of Heterojunctions. Rectangular parallelepiped single-crystal samples were cut with the large faces of either the (l00), (110), or (111) orientation. The remaining four surfaces were also cut to specific orientations to permit accurate relative orientation of the GaAs-Ge pairs. The

Jan 1, 1965

By A. P., Svenningsen

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

Jan 1, 1942

A discussion of the paper by Mr. Campbell, which was read by title at the Lake Superior meeting, but first presented at the New York meeting of the Iron and Steel Institute, October, 1904 (see p. 772). These papers are here published onder a mutual agreement between the Councils of the two Institutes, and will also be found in the Journal of the Iron and Steel Institute for the year 1901, vol. ii. Mr. William R. Webster, Philadelphia, Pa., said: We are under great obligation to Mr. Campbell for his exhaustive investigation, and the results he has put before us to-day. They are the most conlplete series of tests that have ever been made, where all the conditions of rolling, etc., were kept uniform. In discussing Mr. Campbell's first investigations, I claimed first, that the method of least squares, then used, would of necessity only gire the average value of any element, and that if the effect of any element was greater in the presence of high carbon than with low carbon this would not be shown by the method of least squares. Secondly, that the effect of manga nese should be considered on acid steel as well as on basic steel, instead of ignoring all the eff'ect of that element when it was below 0.60 per cent., as was then recommended by Mr. Campbell. I am pleased to note that the results of his present investigation confirm my views on these points. In presenting the results of his first investigation, Mr. Campbell referred to my investigation of 1893-94, and took exception to the value of phosphorus varying (depending on the amount of carbon present) from 800 to 1,500 lb. for each 0.01 per cent. He claimed that one might just as well consider the effect of phosphorus as being constant, and of carbon varying. I refer to this, as he now has introduced very similar conditions in his present tables, in that he gives variable values for manganese (depending on the amount of carbon present) for both acid and basic' steels. Can we now say, with more certainty than formerly, which element should be considered as haviup a constant effect ? There is one other point that I took up in my former discus-

Jan 1, 1905

By Henry Howe

FIG. 1 shows a volute aging break which developed spontaneously in a hardened and tempered steel helmet between 19 and 38 days after it had been tested ballistically. A similar break, shown in Fig. 2, developed spontaneously in a similar helmet about 40 days after the ballistic testing. In this case the rupture occurred abruptly and with a loud report. The path of rupture in this second case, though much the less regular, is the more interesting of the FIG. 1. FIG. 2. two, in that it is an approximation to two parallel volutes centered at the point of impact of the projectile, just below D. Several weeks later, after the photograph for Fig. 1 was taken, a similar doubling of the volute crack occurred in this helmet, starting from the end of the eyelash crack near A and spreading thence to the left contra-clockwise for about ½ in. The negatives from which these pictures are made have not been touched up in any way, save writing the letters on them. In both cases the trajectory of the bullet was normal to the initial surface at the point of impact, and in both the helmet passed the ballistic

Jan 2, 1919

Jan 1, 1910

By J. P. Witherow

The Clapp and Griffiths steel-process may be considered a pneumatic system, similar to the Bessemer, with the difference that the converter is fixed or non-tilting, and that the blast is introduced around the lower section of the converter instead of through its bottom. Mr. Griffiths was engineer-in-chief of the Gilchrist & Thomas basic dephosphorizing process during all the time those gentlemen were experimenting and working up their system, as Mr. G. communicated to me. After separating from these gentlemen, he began developing the present Clapp and Griffiths type of converter. Dr. Clapp, of Nantyglow, Monmouthshire, was a prominent physician in a large iron district. Previous to his association with Mr. Griffiths, he took out some patents on a process of his own for the manufacture of steel, which patents stood in Mr. Griffiths' way; hence the consolidation. Early in the summer of 1883, my attention was called to the experiments of Messrs. Clapp & Griffiths in Great Britain by a friend who had just returned from England. Later in that summer I went to Newport, on the border of Wales, where I met Messrs. Clapp and Griffiths and their friends. After visiting two small converters of their type which were in operation at different works, and spending a few days in the iron-districts of Wales, I went to London, where I met my friend Henry W. Oliver, Jr., who had already heard of the new steel-process. We decided to revisit Wales and examine more fully the process, more especially that Mr. Oliver might have the opportunity of coming practically in contact with the men and die process himself, so that his judgment might not be influenced by my sanguine feelings. On

Jan 1, 1885

By F. V. Shallcross

Physical properties of thin films of CdS and CdSe formed by vacuum deposition onto glass sibstrates have been studied as a function of deposition and processing conditions. The crystallinity and surface features of CdS films were examined using electron microscopy and electron and X-ray diffraction techniques. The films were poly crystalline; the preferred orientation and crystallite size increased with film thickness, substrate temperature, and deposition time. The CdS films consisted primarily of hexagonal-phase material, in contrast to similarly prepared CdSe films which have previously been observed to contain mixtures of cubic and hexagonal phases. As-deposited CdS films showed no major dependence of Hall mobility on crystallite size or degree of preferred orientation. Hall mobility and carrier concentration in CdS and CdSe .films were measured at various temperatures; both parameters increased with temperature and yielded activation energies which depended on fabrication conditions. Surface-desorption phenomena and overcoating of the semiconductor with SiO affected the observed electrical properties significantly. THIN films of cadmium sulfide1,2 and cadmium sele-nide3,4 have been employed by various workers as semiconductors in the insulated-gate thin-film field-effect transistor, known as the TFT. These devices are most commonly made by vacuum deposition of all materials onto an amorphous substrate such as glass. A knowledge of the microstructure and electrical properties of semiconductor layers used in the thin-film transistor is essential in order to form a realistic model for the device and to improve its performance, reproducibility, and reliability. This paper will describe studies of the physical properties of vacuum-deposited CdS and CdSe films prepared under various conditions. Structural characteristics examined in- cluded phases present, crystallite size, nature of preferred orientation of crystallites, surface roughness, and structural homogeneity throughout the film thickness. Electrical properties measured were Hall mobility and conductivity and their dependence on temperature and ambient. Thin-film properties are affected by many fabrication parameters including purity and physical form of evaporant, deposition rate, film thickness, design and temperature of the evaporation crucible, geometry of the deposition chamber, nature of the residual atmosphere, composition and temperature of the substrate, and details of postdeposition processing. PREPARATION OF FILMS In this work the semiconductor films were deposited in a conventional oil-diffusion-pumped system with pressures in the 10-8 torr range. The CdS evaporant was obtained from the Eagle-Picher Co. as a high-purity coarse-grained crystalline powder; the CdSe was a high-purity sintered powder supplied by the Harshaw Chemical Co. The evaporation crucible was a resistance-heated molybdenum-wire basket coated with aluminum oxide and filled with a quartz wool plug at the top. The source to substrate distance was usually 10 cm. This region was enclosed by a Pyrex inner cylinder. The substrate was heated with an overlying Pyrex plate coated with tin oxide. The substrate temperature was controlled using a thermocouple attached to the lower side of the heater. This thermocouple was calibrated against another thermocouple attached to a dummy substrate and by observation of melting points of various metal films deposited in the system. The substrates were polished borosilicate glass plates and conventional glass microscope slides. Substrate preparation included cleaning with an ultrasonically agitated detergent bath followed by isopropanol-vapor de-greasing. Film thickness was measured interferomet-rically during and after deposition. STRUCTURE OF CdS FILMS Structural studies were performed on CdS films using electron diffraction, electron microscopy, and

Jan 1, 1967

By H. F. Bishop, F. A. Brandt, W. S. Pellini

The solidification mechanism of experimental steel ingots (7x7x20 in.) was studied by thermal analysis. It was determined that solidification proceeds in wave-like fashion at rates which are determined by the carbon level, superheat, and mold thickness. The thermal cycles of the mold walls were related to the course of solidification. ESPITE marked advances in the field of solid state transformation, metallurgical research has contributed comparatively little exact quantitative data on the mechanism of solidification of metals. There is, therefore, a great need for such data in the various metallurgical industries. The mechanics of solidification of ingots have been investigated in the past primarily by studies of the rate of skin formation as indicated by bleeding or "pour out" tests. The "pour out" method, however, is a tool which gives only approximate information. In the case of alloys with wide solidification ranges, such as irons and certain nonferrous alloys, the method will not work at all; in the case of alloys of intermediate solidification ranges, such as commercial steels, the information may be misleading. Thus, the general adoption of this method has resulted in divergent conclusions regarding the solidification process. Chipman and Fondersmith1 by means of bleeding tests have shown that the linear growth of a solidifying ingot wall follows a parabola of the general form, D = K C, with the start of solidification delayed until superheat is exhausted, as indicated by the constant C. These tests were carried only to a wall thickness of about 5 in. using an ingot of approximately 17x39 in. in cross-section; hence the latter stages of solidification were not studied. Matuschka2-3 indicated that linear solidification of ingots is rapid at first, then slow, but toward the end of solidification the rate becomes extremely rapid again. Spretnak's4 bleeding studies indicated that, wall growth is expressed more rigorously by two parabolas, and that their point of intersection corresponds to a change of solidification mode from columnar to equiaxed. Spretnak also showed that the K values of the first parabola are always the same regardless of superheat. Nelson bled ingots of square cross-section and found that linear wall growth is initially rapid but decreases continually until the end of solidification. He also concluded that rate of solidification in ingots of square cross-section increases 2.15 pct for every 10 pct increase in cross-sectional area of the mold. The mold ratios considered (ratio of cross-sectional area of the mold to cross-sectional area of the ingot) were all less than 2 to 1. The subject of solidification has also been treated mathematically in many cases, but because of the lack of accurate thermal constants and the simplifying assumptions required, as their authors generally acknowledge, they represent only approaches to the actual conditions of ingot solidification. A third method of studying solidification is the electrical analogue method promulgated by Pasch-kis6-7 and by Jackson and coworkers.8 This method treats solidification as a heat transfer problem with the solidification cycle synthesized on an electrical circuit. Paschkis in his treatment of solidification considered the fact, which was generally ignored, that solidification of steel is not simply the growth of a plane solid wall but a more complex process occurring over a temperature range as indicated by the constitution diagram. Undoubtedly, the anomalous results obtained by bleeding tests arise from the inability to measure quantitatively this mushy condition. The shape of Paschkis' solidification curves are more nearly in accord with those of Matuschka, in that they indicate rapid linear solidification at the beginning and end of solidification with intermediate solidification occurring at a slower rate. Paschkis indicates a definite lengthening of solidification time with increasing superheat. Thermal analysis is a direct method providing exact information for all types of metals regardless of solidification range and was thus adopted in the present program to follow the entire course of solidification from the surface to the centerline of the ingots. The method has the added advantage of being adaptable to following the thermal cycle of the ingot mold during the course of solidification. Test Methods The ingots studied were of square cross-section, 20 in. long, tapered from 71/4 in. at the top to 63/4 in. at the bottom, and fed with a hot top 7 in. in diam and 12 in. high. The molds were uniform in wall

Jan 1, 1953

By J. J. Becker

BEAN1 has discussed the magnetic behavior of mixtures of small ferromagnetic particles on the order of 20 to l000A in diam. As he points out, there are three size categories with characteristic properties: 1) Particles large enough to contain many ferromagnetic domains magnetize initially by the motion of domain walls. The initial susceptibility of such particles, if domain-wall motion is assumed to be perfectly easy, depends only on their shape. It is equal to the reciprocal of the demagnetizing factor (and is thus 3/4 tt for a sphere) and is independent of temperature. 2) Smaller particles find it energetically undesirable to contain domain boundaries. They are always spontaneously saturated, and reverse their magnetization only by rotation of their entire magnetic moment. As assemblage of such particles has a remanence which is a large fraction of the saturation of the assemblage; its coercive force is on the order of 2K/1,, where K indicates magnetic aniso-tropy from any source, and I, is the saturation magnetization of the substance of which the particles are made. 3) Particles which are still smaller continue to be single-domain, but the direction of their magnetization fluctuates thermally, as first pointed out by Neel.' They have no remanence and no coercive force and possess the temperature-dependent magnetization curve of a paramagnetic substance with a very large moment. Bean calls this superpara-magnetism. All of these kinds of behavior are observable in alloys consisting of a precipitate of ferromagnetic phase in a nonferromagnetic matrix. Fig. 1 shows a typical aging curve for the room temperature coercive force of a sample of 98 pct Cu-2 pct Co alloy

Jan 1, 1958

By P. H. Metzger, D. W. Fuerstenau

The activation of sphalerite was found to occur at a much lower rate with Pb++ then with Cut++ or Ag+. To prevent activation with Pb++, the ratio [m in solution must approximate 103. An example is given illustrating how this condition is met in practice through the addition of zinc sulfate and soda ash. In selective lead-zinc flotation, the mill operator, especially the one who is concentrating a partially oxidized ore, often must add zinc sulfate and/or soda ash for effective depression of the sphalerite. In the present paper the authors show how this practice prevents the activation of sphalerite in the presence of Pb++. A number of years ago Gaudin (1) postulated that Zn++ might control the activation of sphalerite with Pb++ through competitive adsorption. However, recent experimentation has shown the activation of sphalerite with Ag+ and Cut++ to be a chemical reaction in which silver or copper ions replace zinc in the sphalerite lattice through the formation of a more insoluble sul-fide (2,3,4) Thus, if activation with Pb++ is similar to that with Ag+ or Cu t+, zinc salts should control the activation of sphalerite not through competitive adsorption but because the ratio of [zn++/Pb++] in solution regulates the extent of the chemical exchange between Zn++ and Pb++ in the solid phase. The objective of this investigation has been to study the kinetics and equilibrium conditions for the uptake of Pb++ by sphalerite and to investigate the prevention of lead activation with zinc salts. BASIC PRINCIPLES Sphalerite activation has been shown to be a replacement reaction wherein a less soluble compound is formed at the expense of the more soluble zinc sul-fide (2,3,4) For example, if sphalerite is placed in an aqueous silver nitrate solution, ZnS gives to the solution more S= than can exist together with Ag+, and hence the following reaction takes place: ZnS + 2 Ag+? Ag2 S + Zn ++; k = [zn ++]/[Ag ++]2 = 10 26 (1) Therefore, ZnS will dissolve in the presence of Ag+ and activation of sphalerite with Ag+ will proceed after monolayer coverage by solid state diffusion until equilibrium conditions are reached in the system (2, 4) Because of the large difference in the solubility of ZnS and Ag2S, zinc salts cannot affect the reaction unless a complexing agent, such as cyanide ions, is present to complex Ag+ more tightly than Zn++ . By complexing Ag+ and Zn++ in solution, the uptake of Ag+ by sphalerite can be regulated by controlling the ratio m. . Experimentally (2) it was found that the activation of sphalerite by Ag+ could be prevented through the addition of NaCN if this ratio reached a value of approximately 10 26. The mechanism of sphalerite activation with copper salts is given by the following reactions: ZnS + Cu ++ ? CuS + Zn + + ; (2) k = [Zn++]/[Cu++] = 10 11 ZnS + Cu + ? Cu2S+ Zn++; (3) Experimentally Mao (3) found that the activation of sphalerite with Cu++ or Cu + was prevented if the ratios expressed in Equations 2 and 3 were approximately l09 and l022, respectively, with cyanide ions as the deactivator. Although zinc salts do not affect the activation of sphalerite with silver or copper ions in the absence of a complexing agent, activation with lead ions theoretically can be controlled by the addition of zinc salts because of the relatively small differences between the solubility of ZnS and PbS (5). Equilibrium

Jan 1, 1961