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By L. H. Wolfe, J. O. Thieme

The tensile and shear strengths of frozen soil and the compressive strengths of ice and frozen soil were measured These tests showed that the strength of ice and of frozen soil increased as the temperature was decreased. A method is presented for the measurement of thermal conductivity and specific heat of earth and ice. Using the parameters thermal conductivity, specific heat and density, the thermal diffusivity was calculated. Results of thermal property tests establish water as the major variable contributing to thermal property values. INTRODUCTION During the last few years, a considerable interest has developed in underground storage of cryogenic liquids such as liquid natural gas. Because of its economy and safety, underground storage is being used. Before underground caverns could be seriously considered, however, the strength and thermal characteristics of the soil had to be obtained. Methods are presented herein for measuring tensile, compressive and shear strengths, specific heats and thermal conductivities. The tests were performed on two soils at temperatures from ambient to -195C. Because it is difficult to find data in the literature that pertain to a particular soil, ice was used to evaluate some of the experimental procedures. Some of our ice data are compared to the published values. PHYSICAI, PROPERTIES SOIL SELECTION AND SAMPLE PREPARATIONS The physical and thermal tests were performed on recompacted samples of two typical soils that might be encountered in underground caverns: a gray, fire clay that had been pulverized and mixed with water into a pliable mud; and a brown, sandy silt that was dug from a dry river bank and subsequent1y mixed with tap water. The moisture content of the test specimens was 17 to 22 per cent (based on the wet weight of the soil). This amount of water nearly saturated the silt, but the clay was well below the saturation point. The soils are partially described by the sieve analyses (Fig. 1) which show the particle size distribution of the coarser than 44 micron portion of the soils. The curves also show that approximately 75 per cent of the clay and 20 per cent of the silt are finer than 44 microns. The particle size seems to affect some of the physical properties, and the finer than 44 micron portion is important in the thermal conductivity test. Physical specimens were cut with a bandsaw from frozen blocks of the soil. The specimens were then sanded and kept frozen until after they were tested. They were stored at the approximate test temperature for several hours. Then, to equilibrate the samples to the test temperature, they were stored at the temperature at least an hour before they were tested. TEST EQUIPMENT An Instron, which is a constant speed gear-driven instrument, applied force to the samples and drew stress-strain plots of the test. All of the samples were strained at 0.02 in./min. All of the physical tests were conducted in a temperature cabinet that controlled the temperature to 1C. TENSILE STRENGTH Briquette or "dog-bone" shaped tensile specimens were pulled with suitably shaped jaws. This shape of specimen, which is usually used for tensile tests of concrete, is satisfactory for testing frozen soils except that the samples tend to

Jan 1, 1965

By Howard N. Eavenbon

The low-volatile, or smokeless, coal field of southern West Virginia is in Fayette, Raleigh, Wyoming, Mercer, Summers and McDowell counties, in the extreme southern portion of the state, and extends into the adjacent counties of Tazewell and Buchanan in Virginia. McDowell County is the largest producer, with Fayette and Raleigh counties next. The total area of the field (Fig. 1) is approximately 1600 square miles, or 1,024,000 acres. The percentage of volatile matter in the various seams ranges from 15 to 26 per cent, The upper limit of true low-volatile coal is usually considered to be 23 per cent volatile matter; above this point, the coal usually is classed as medium volatile. This limit will be used in this paper. Geological Position of Seams The smokeless seams are among the oldest coal seams in the country, as the Pocahontas group of rocks is the lowest member of the coal-bearing series and rests on top of the Mauch Chunk red shale, in or below which no coal seams of any importance occur. The Pocahontas group, or Lower Pottsville measures, has a thickness of 750 ft. in southern McDowell County, which decreases to about 350 ft. at Prince, on the New River, in Fayette County, 50 miles to the northeast. In this group, at various points, 12 coal beds have been found, of which 4 have been found in workable thickness and are now being mined. The New River group, or Middle Pottsville measures, is just above the Pocahontas group and varies in thickness from 1300 ft. in southern McDowell County to about 700 ft. along New River. At various places, 16 beds of smokeless coal have been identified in this group, of which 5 have been found in workable thickness and are now being mined. A general columnar section of these strata is shown on Fig. 2. The workable seams in these strata, arranged in geological sequence, are as shown on page 77.

Jan 1, 1932

By William F. Harris, Joseph Easha

FOR many years basic control of refinery operations depended on visual observation of small chill specimens poured at various intervals during processing. The oseto of these samples was related to the physical and chemical properties of the metal. Since the =setn is dependent on many factors other than oxygen content, this method, while giving a general indication of the condition of the copper, does not accurately measure the oxygen content. For the last 3 years a modified vacuum fusion procedure which enables the operator to determine the oxygen content of the copper within 1 5 min of sampling has been in use at the Westinghouse Copper Mill. For use with this apparatus a sampling technique has been developed which gives oxygen values representative of the oxygen content of the wire bar. The sampling technique is based on a statistical study, which compared the oxygen content of the laboratory sample of copper poured at the same time a wire bar was being poured, with the oxygen content of the wire bar. The apparatus used for the determination of oxygen in copper is shown in Fig. 1 and is essentially the same as previously described but with one important modification. A very porous fritted glass disc has been inserted in the tubing between the manom- eter and 40/50 ground glass joint. The fritted disc retains the copper vapor and copper particles in the furnace section and prevents contamination of the mercury in the manometer. Without the disc the manometer became difficult to read after a few weeks of operation. In earlier work1 it had been established that the simplified vacuum fusion apparatus used at the Copper Mill gave essentially the same results as a con-vential vacuum fusion apparatus. However, for this study it was necessary to determine the difference, if any, between the oxygen content of the wire bar and the oxygen content of the small chill sample used for the oxygen analysis. This correlation was established by taking a chill sample at the same time wire bars were being poured. The wire bar being poured at the time the chill sample was taken was marked and removed for further analysis. The copper is sampled at various times during refining and cast into laboratory size samples with the mold shown in Fig. 2. The mold is made of cold rolled steel and is 2 in. high and 2 1/2 in. in diam. The large upper portion of the cast sample is used for measurement of the conductivity of the copper, The lower portion which is a rod about 1/4 in. diam by 3/4 in. long is used for determination of the oxygen content. This portion of the sample weighs about 5 g which is approximately the size sample used for the analysis. The only preparation neces-

Jan 1, 1962

By Wei-Kao Lu

A general rate equation is derived for gas -solid reactions in metallurgical processes by considering the contributions of chemical reaction at inter-phase boundaries and diffusion through the solid product layer simultaneously. This equation takes care of the whole range continuously from purely diffusion control to purely chemical reaction control. The parabolic law,' McKewan's equationa derived with the assumption of interface area control and the equation derived by Kawasaki et al. with the assumption of purely diffusion control are found as the limiting cases of the corresponding forms of the general rate equation. Many metallurgical processes involving gas-solid reactions have been extensively studied. The common examples of these processes include the reduction of oxides to metallic products, the roasting of sulfides to oxides or chlorides and the oxidation of metals. Gas-solid reactions consist of at least two kinds of steps; one involves the transport of reactant and product to and from the reaction zone and the other is the chemical reaction taking place at the interphase boundaries. In the limiting cases one or the other of the above mentioned steps will be much slower than the other and is then rate controlling. For example, the oxidation of metals is diffusion controlled and obeys the parabolic law.' On the other hand, if the diffusion rate is much larger than the chemical reaction rate then it will be controlled by the chemical reaction rate. This latter case occurs for the reduction of iron oxides studied by McKewan. If the rate of diffusion and of the chemical reaction have the same order of magnitude, a more detailed analysis is necessary. Thus at the beginning of the reaction when the solid and gaseous reactants are in direct contact, the reaction should be chemical reaction rate controlled as no diffusion process is involved. At the other extreme as the reaction zone moves further into the solid, the diffusion distance becomes greater and the diffusion rate continuously decreases. Eventually, therefore, for a sufficiently large sample the rate must become diffusion controlled. As the transition from one controlling step to the other must be continuous, we cannot describe this transition period by either of the two limiting cases. In this paper the author attempts to derive a general rate equation for gas-solid reaction systems. This is effected by considering the rates of diffusion and chemical reaction simultaneously from the state of pure diffusion control to pure chemical reaction control. I) DERIVATION The system under consideration is made of at least three phases, namely the gaseous one, the solid reactant, and the solid product as shown in Fig. 1. The notations are listed at the end of the paper. The mass transfer process involves the diffusion of reactants and products across the solid product layer. It is reasonable to consider that no chemical reaction will take place in the solid product layer with respect to both gaseous reactant and product. For the characteristics of local equilibrium of the system, the diffusion process is really in a quasi-steady-state. It will be proved in the following paragraphs. Then we can invoke the law of conservation of mass valid for all chemical species passing through the layer. The solid reactant sphere has an initial radius, ro, after a fraction of completeness of the reaction, the unreacted core has a radius ri, where r, is in the solid product region. Let Cg be the activity of gaseous reactant in the

Jan 1, 1963

By J. H. East, E. R. Maize

Probably no other type of equipment is now being introduced into American underground mines about which less is known and about which there is more misinformation than the Diesel mine locomotive. Any equipment installed underground brings with it hazards that were not present before, and it is the purpose of this paper to show that Diesel-powered equipment can be used with safety in underground mining if certain feasible but very important precautions are taken. Diesel locomotives are not new in underground mining, since they have been used successfully in European mines for at least 19 years, but their use in American mines is exceedingly limited; so far as is known, only five Diesel mine locomotives are operating at present in United States mines. Diesel locomotives were permitted underground in Great Britain for the first time in 1939, and the rapid increase in the number in use in those mines testifies to their safety and efficiency. More than 1300 Diesel mine locomotives are in use in European mines, according to the latest statistics; these locomotives are employed in coal, iron, lead-zinc and mercury mines. SO far as is known, the Diesel mine locomotive has not yet caused an explosion or mine fire, and has not been the cause of any fatalities from toxic gases in the mines in which it has been used. Adjustments of Diesel Engines foR Underground Use A Diesel engine adjusted to work in an underground mine should not be confused with the same engine adjusted for use outside the mine. Adjustment of the air:fuel ratio for engines that are used on the surface is intended to give the maximum fuel economy, and little or no attention is given to the chemical composition of the exhaust gas produced. Many such engines are poorly adjusted and perhaps poorly maintained, with the result that the engine emits smoke in quantity as well as the disagreeable odor familiarly associated with Diesel engines. The air:fuel ratio in the case of Diesel engines operated on the surface is generally around 15:1; that is, 15 lb of air to burn I lb of fuel. Diesel engines adjusted to work underground usually have an air:fuel ratio of about 20:1, as at this ratio the minimum quantity of toxic gases is given off in the engine exhaust. Diesel engines operated underground must be maintained in better condition than similar engines used on the surface; otherwise, the smoke emitted in the exhaust becomes objectionable if not unendurable. Practically normal air is required for safe operation of Diesel engines underground or in confined places; failure to provide virtually normal air for Diesel engine operation is almost certain to result in trouble. Bureau of Mines engineers have determined that the air in which a Dicsel Operates hi confined places should contain less than % pct of carbon dioxide and at least 20 pct of

Jan 1, 1949

By A. B. Parsons

Not so many years ago the interest of the average mining engineer in money matters-aside from his pay check or his consulting fees-was confined to the per-ton cost of mining and beneficiating ore and to the amount of capital that would be required to erect the plant necessary to carry out such operations on a prescribed scale. The so-called "business men" assumed that questions of marketing the products, of profits, and of dividends were in their exclusive sphere-matters too intricate or, perhaps, too practical for the mere engineer! In the case of a new enterprise, the promoter shouldered the entire responsibility for raising the necessary funds, and incidentally he got the lion's share of profits. In fact, he frequently profited handsomely even though the mine earned little or nothing. Occasionally the engineer turned promoter or entrepreneur--conspicuous examples are Herbert Hoover, D. C. Jackling, William Braden and F. W. Bradley- but by and large he remained in a sphere of his own. To what extent this condition of affairs has changed is difficult to say. It might be argued that it were better that it be not changed; and yet I cannot help feeling that in mine promotion lies a distinct opportunity for the

Jan 1, 1932

By J. R. Thoenen, M. C. Malamphy, G. K. Dale

The beginning of the war and the events leading up to it precipitated a near crisis in the aluminum industry. Demands for the metal reached proportions far beyond the prewar production capacities and, in addition, the submarine menace seriously curtailed the importation of bauxite from South America, hitherto a chief source of high-grade ore. The situation required an intensive search for domestic ore to augment the reserves and in October 1941 Congress directed the Department of the Interior to investigate the extent, mode of occurrence, and quality of bauxite in the United States. In December of that year the Bureau of Mines and the Geological Survey began the search for bauxite in Arkansas, where more than go per cent of the domestic ore had been produced and where the greatest amount of bauxite was known to occur. The program involves the geophysical and geological investigation of the Arkansas bauxite region and the core drilling of areas considered favorable for the occurrence of bauxite deposits. Cores taken from the bauxite-kaolin zone are sampled and analyzed in the Bureau of Mines laboratory in Little Rock. The information from each of the deposits discovered is then assembled, the bauxite is graded with respect to its possible utility, tonnage estimates are made, and the whole is presented in the form of a war minerals report. Thirty-eight new bauxite deposits had been discovered and investigated at the end of the calendar year 1944, and the presence of several others had been indicated by the drilling. More than 5000 holes had been drilled throughout the bauxite region, and more than 60,000 chemical analyses had been made of samples taken from the bauxite-kaolin zone. A study of the chemical analyses led to certain general conclusions not only with regard to the chemical composition of Arkansas bauxite, but also with regard to its component minerals. Charts and diagrams based on these conclusions have been developed for practical use by the Bureau of Mines: (I) to serve as a check against laboratory analyses, (2) to present tonnage estimates of ore bodies based on mineral composition, (3) to illustrate the relationship of tonnages of bauxite to the alumina, silica, and iron content, and (4) to serve as a control for mining operations by providing a means for quick estimates of the value of the ore from a partial analysis of its chemical constituents. The use of charts and diagrams similar to those discussed in this paper-- is not new. The use of the trilinear diagram for studying the ultimate analyses of coals as of proposed by Ralston in Bureau of Mines Technical Paper 93 (1915) showed that the various ranks of coal fell in different areas on the diagram and that volatile matter, calorific value and other properties could also be plotted by the use of contours. A considerable subsequent literature, largely on classification of coals, has accurnulated since then, showing the utility

Jan 1, 1948

By J. R. Thoenen, M. C. Malamphy, G. K. Dale

The beginning of the war and the events leading up to it precipitated a near crisis in the aluminum industry. Demands for the metal reached proportions far beyond the prewar production capacities and, in addition, the submarine menace seriously curtailed the importation of bauxite from South America, hitherto a chief source of high-grade ore. The situation required an intensive search for domestic ore to augment the reserves and in October 1941 Congress directed the Department of the Interior to investigate the extent, mode of occurrence, and quality of bauxite in the United States. In December of that year the Bureau of Mines and the Geological Survey began the search for bauxite in Arkansas, where more than go per cent of the domestic ore had been produced and where the greatest amount of bauxite was known to occur. The program involves the geophysical and geological investigation of the Arkansas bauxite region and the core drilling of areas considered favorable for the occurrence of bauxite deposits. Cores taken from the bauxite-kaolin zone are sampled and analyzed in the Bureau of Mines laboratory in Little Rock. The information from each of the deposits discovered is then assembled, the bauxite is graded with respect to its possible utility, tonnage estimates are made, and the whole is presented in the form of a war minerals report. Thirty-eight new bauxite deposits had been discovered and investigated at the end of the calendar year 1944, and the presence of several others had been indicated by the drilling. More than 5000 holes had been drilled throughout the bauxite region, and more than 60,000 chemical analyses had been made of samples taken from the bauxite-kaolin zone. A study of the chemical analyses led to certain general conclusions not only with regard to the chemical composition of Arkansas bauxite, but also with regard to its component minerals. Charts and diagrams based on these conclusions have been developed for practical use by the Bureau of Mines: (I) to serve as a check against laboratory analyses, (2) to present tonnage estimates of ore bodies based on mineral composition, (3) to illustrate the relationship of tonnages of bauxite to the alumina, silica, and iron content, and (4) to serve as a control for mining operations by providing a means for quick estimates of the value of the ore from a partial analysis of its chemical constituents. The use of charts and diagrams similar to those discussed in this paper-- is not new. The use of the trilinear diagram for studying the ultimate analyses of coals as of proposed by Ralston in Bureau of Mines Technical Paper 93 (1915) showed that the various ranks of coal fell in different areas on the diagram and that volatile matter, calorific value and other properties could also be plotted by the use of contours. A considerable subsequent literature, largely on classification of coals, has accurnulated since then, showing the utility

Jan 1, 1948

By E. I. Larsen, E. F. Swazy, F. R. Hensel

Experience has indicated that hard bronzes are not suitable for bearing applications where high bearing loads and speeds are involved. It is the general practice to utilize softer materials for these purposes, such as copper, lead, silver, babbitt, lead-base alloys, and more recently aluminum-base alloys, preferably supported by a steel backing. It was the objective of the present investigation to study a new material produced by powder metallurgical methods susceptible to precipitation-hardening. Test MAteriaIs Preliminary tests were made with compacts containing copper, nickel and silicon in quantities sufficient to form 3 to 5 per cent nickel silicide. It mas found that this type of alloy was susceptible to the formation of a soft surface shell when sintered in tank hydrogen. The depth of the shell depended On the length of sintering time and sintering temperature, and varied in thickness from a few thousandths to as much as One eighth inch. This soft shell resulted from the preferential oxidation of silicon, thereby reducing the efficiency of age-hardening by the nickel silicide compound. The body of the sintered compacts below the soft shell could be precipitation-hardened to a hardness of 70 to 85 Rockwell B, by quenching from goo°C. and age-hardening at 450°C. A series of tests was made with various addition agents, in order to decrease the rate of preferential oxidation, and it was found that phosphorus was most beneficial in this respect. After considerable experimentation, the following nominal com-position was accepted as standard: 2.4 per cent nickel; 0.8 silicon; 0.3 phosphorus; balance copper. The physical propertties and certain bearing properties of this alloy are described in the present paper Preparation of Compacts Several methods of incorporating the hardening ingredient (nickel silicide) were studied. Compacts formed from copper, nickel and silicon powders were found to be inferior to those fabricated from prealloyed nickel silicide master alloys, because of the rapid oxidation of pure silicon during sintering. The use of a prealloyed nickel silicide hardener containing 25 per cent silicon and 75 per cent nickel could be further improved by preparing a master alloy, incorporating nickel, silicon, phosphorus and copper, having the following nominal composition~ 25 per cent nickel; 7 silicon; 3 phosphorus 64 copper. This alloy is brittle in the cast condition and can be readily powdered. Sintering Procedure The blended powders were pressed at '5 to 40 tons per sq' in., the pressure depending on the size and shape of the compacts. Sintering was carried out in hydrogen or cracked ammonia atmospheres at

Jan 1, 1946

By Irving B. Cadoff, Ernest Levine

The fracture path in a Cu-4 pct Ag alloy wet with mercury was found to he dependent on the heat treatment used prior to tensile testing. Both quenched and slow-cooled alloys were embrittled by the mercury.. For quenched alloys, which were single -phase, the crack path was intergranular. Slowly cooled alloys, which contained precipitate platelets, exhibited transgranular fracture. By comparing stress-strain data for these alloys with similar data on mercury -embyittled solid-solution alloys, it was found that the role of the precipitate and that of the grain boundary in the fracture process were equivalent . THE fracture path which results when metals are strained in a liquid environment appears to be dependent upon the nature of the specific system. Mixed transgranular and intergranular cracking has been observed in the 2024 T4 aluminum alloy when wet with a Hg-Zn amalgam.' Transgranular fracture was induced in an A1-4 pct Cu alloy by masking off the grain boundaries from the liquid Hg-Zn amalgam.' The embrittlement of solid-solution alloys of copper in mercury results in intergranular fracture.' The effect of a precipitated phase on the fracture path in copper alloys is the subject of the present investigation. Cu-4 pct Ag was chosen so that its behavior could be compared with previous work on embrittlement of copper alloys. PROCEDURE High-purity copper (99.999 pct) was used as a base metal, along with 99.999 pct purity silver. Melting was carried out in graphite crucibles with manual agitation to get adequate mixing. The ingots were homogenized by means of vacuum annealing, chemically cleaned, and cold-rolled with intermediate vacuum anneals, to the desired thickness of 0.025 in. The rolled sheets were sheared to the final specimen size of 1 by 0.025 by 0.1 in. The specimens were then electropolished in phosphoric acid (concentrated) and heat-treated in an evacuated capsule at the solution temperature of 770°C. One batch was slow-cooled and the other quenched in water. The thermal etching which occurred during heat treatment was sufficient to permit grain boundary and precipitate delineation. Tensile tests were carried out in air and in mercury on a Table-Model Instron at a pulling speed of 0.2 in. per min. Wetting was accomplished by electro-polishing in phosphoric acid, rinsing in alcohol, and immersing in a pool of mercury. Once wet the coating was stable throughout the mechanical tests. In our studies it was found that wetting the surface or total immersion in mercury produced identical results. For convenience, the wetting technique was used for the experiments described. The crack pattern was observed directly on the surface by removing the mercury after testing. De-wetting was accomplished by flame heating the samples in a vacuum after testing and before observation of the surface. No etchant or polishing was used so as not to obscure the crack pattern on the surface. The mercury removal, however, resulted in a pitted surface but otherwise left the pertinent features visible. Photomicrographs were taken in this condition so as not to disturb the structure associated with the crack pattern. The average precipitate spacing was measured previous to coating the sample with mercury by use of an optical eyepiece micrometer. RESULTS The microstructure of the quenched specimens was single-phase while that of the slow-cooled specimens contained thin platelets of a second

Jan 1, 1964

By P. D. Southgate

VIBRATION, both ultrasonic and sonic, can affect the course of a variety of metallurgical processes. Reports of work on this subject have appeared at intervals over the last twenty years and a thorough review has been made by Hiedemann,' who gives a full list of references. It has been established that both refinement of structure and outgassing of the melt can be produced in most metals with sufficiently intense vibration. Many of the experiments in this field have been carried out using alloys of direct commercial interest in production- type casting equipment. Here a different approach is adopted, and simple binary alloys which exhibit different types of structure are used to facilitate examination of the effects produced under well-controlled conditions. Results from this kind of experiment should enable the basis of larger scale experiments with similar types of materials to be better substantiated. The alloys selected for this work are: 1) aluminum of 99.2 pct purity, the principal impurity being iron, near 0.4 pct; 2) A1-1.8 pct Fe, which is near eutectic composition; 3) A1-4 pct Fe—the second phase, of composition FeAl3, forms distinct acicular crystals; and 4) A1-12 pct Si—although this is of eutectic composition, the silicon normally appears in the form of large plates. Experimental Method There are three practicable methods by which acoustic vibration can be transferred to liquid metals: a) vibration of the whole of the container; b) electromagnetic induction; and c) insertion of a vibrating probe into the liquid. Method c is chosen here, and a frequency of 8 kc per sec is used. The end of the probe is electrically heated so that the metal near it will be the last to solidify. This ensures that vibration is transmitted directly to the liquid metal without passing through any solidifying and pasty intermediate region, which would attenuate acoustic waves severely. In addition, the heating prevents solid metal adhering to the probe, with consequent detuning. The transducer assembly is shown in Fig. 1. A stack of Permendur laminations 30 cm long acts as a half-wave vibrator and a winding along its length carries polarizing and energizing currents. It is joined by a half-wave coupling bar to a mild steel exponential horn, which tapers from 3.8 to 1.1 cm diam. A stainless steel stub 3 cm in length is welded on the free end. The assembly is supported by a plate located at the node of the coupling bar. Acoustic radiation losses are minimized by allowing the free end of the transducer to protrude above the surface of the cooling water. The exponential horn serves the function of matching the acoustic output impedance of the transducer to the radiation resistance of the probe into the melt. Electrical drive is provided by a 1 kw generator. Measurements of probe vibration amplitude during melt treatment are obtained from a gramophone pick-up with the needle attached to the wide end of the horn. This device is calibrated with a microscope before use. Liquid aluminum is very actively erosive and solution of materials with which the molten metal comes into contactcauses difficulties. Erosion of the probes in particular can be severe since it is greatly accelerated by the vibration. Tests of various acous-

Jan 1, 1958

By J. B. Newkirk, D. L. Martin, A. H. Geisler, R. Smoluchowski

A FUNDAMENTAL investigation of the mecha-nism of the ordering reaction and of the accompanying changes in properties has been undertaken, since an extensive study of this process could well contribute to the knowledge of phase transitions in alloys. Cobalt-platinum alloys were chosen for the study since they exhibit interesting and unusual permanent magnet properties.1,2. In addition, the ordering reaction in cobalt-platinum alloys is a convenient one to study experimentally because of the high maximum ordering temperature, the large difference in the X-ray scattering power of cobalt and platinum atoms, and the relative ease with which the alloys can be plastically worked into wire and strip. In the early stages of this study, it became apparent that the published phase diagrams&apos;, &apos; of the cobalt-platinum system contained questionable features, in the region of 40 to 60 atomic pct Co, which were considered in another publication by the authors.4 That portion of the research reported elsewhere on the equilibrium states of cobalt-platinum alloys does not confirm the presence of a previously reported, high temperature disordered tetragonal phase and a low temperature body-centered cubic phase. On the other hand, the structure of the ordered phase is face-centered tetragonal with an atomic distribution analogous to that of CuAu.4 This lattice forms from the disordered face-centered cubic phase in such an orientation that the <100> directions are parallel to the <100> direc-tions of the disordered phase. At compositions other than the ideal 50 atomic pct the ordered phase can exist in equilibrium at high temperatures with the disordered phase. A Widmanstatten pattern of plate-like particles of the ordered phase parallel to (110) planes of the disordered matrix is observed when an initially disordered alloy is held at these temperatures. The temperature range of the two-phase region has been determined for three alloys by X-ray diffraction analyses, microscopic examination, and electrical resistivity measurements, and these results are incorporated with some of those of Gebhardt and Köster in the revised phase diagram of fig. 1. The purpose of the investigation reported here was to examine the mechanism of ordering in co-balt-platinum alloys by X-ray diffraction and metal-

Jan 1, 1951

By A. H. Larson, T. P. McNulty

RECENTLY, an investigation of the absorption of sulfur dioxide gas in molten binary copper alloys was conducted. A Sieverts-type apparatus, consisting of a mercury-filled gas dispensing buret and a mercury manometer, was used initially for determining the volume of gas absorbed as a function of pressure. The equilibration behavior of the alloys studied indicated that the mercury in the gas measuring system was absorbing sulfur dioxide. Owing to the widespread use of mercury as a displacement medium in absorption studies, an investigation was made to determine the nature and magnitude of the mercury - sulfur dioxide absorption effect. The gas measuring system was modified by substituting a Worden Quartz Products Type PDHV fused-quartz-spiral pressure gage for the mercury-filled dispenser and manometer. The dispensed gas volume at known temperature and atmospheric pressure was measured by evacuating a Pyrex vessel of known volume and by admitting sulfur dioxide into the vessel until the attached quartz pressure gage registered atmospheric pressure. Atmospheric pressure was measured concurrently with a separate mercury barometer. The volume of the empty sample chamber and its attendant apparatus was determined by measuring the equilibrium pressure accompanying the addition of a measured volume of sulfur dioxide into the initially evacuated system. The volume of the mercury sample was calculated from the density of mercury at the temperature of the study (25°C). Measured volumes of sulfur dioxide were then dispensed into the system and the equilibrium pressure accompanying each gas addition was determined. From the difference between the system volume and the mercury volume, the number of moles of gaseous sulfur dioxide remaining in the system at each pressure was calculated. The difference between the number of moles of gas dispensed into the system, denoted Enso2: and the number of moles of gas remaining in the system after absorption equilibrium had been attained, denoted nso2(g), was equal to the number of moles of absorbed gas, denoted nSO2. The number of moles of absorbed gas was then converted to absorbed volume, denoted VSo2, in cu cm at stp conditions of (PC and 760 mm Hg. Table I contains calculated values of Snso2, nSo2(g), and VSo2 for different sulfur dioxide pressures. In the original system, denoted Run I, volume limitations of the gas dispensing system prevented absorption studies at equilibrium pressures near atmospheric pressure, so a different gas dispensing system, denoted Run 11, was used for determining the last pressure reading in Table I. The data in Table I are expressed in terms of the absorption of sulfur dioxide in 49.68 cu cm of mercury. In Fig. 1, these data are expressed in terms of the absorption of sulfur dioxide in 100 cu cm of mercury. Since the absorption data plotted in Fig. 1 show a linear relationship, the volume of sulfur dioxide absorbed in mercury is a function of the first power of pressure. The absorption reaction is So2(gas) = SO2 (in Hg) The first-power pressure dependence, coupled with the fact that the sulfur dioxide could be removed from the mercury by applying vacuum, indicated reversible

Jan 1, 1967

By J. W. Cunningham, W. A. Tiller, D. H. Lane

The effect of ultrasonic vibrations on ingot solidification has been considered both theoretically and experimentally. The theoretical section elucidates the mechanisms by which the ultrasonic vibrations might refine the ingot structure. The experimental section describes a very efficient means of introducing the ultrasonic vibrations to the freezing interface. The application of this technique to the consumable-electrode arc melting process shows that the columnar mode of freezing may be effectively suppressed yielding an ingot structure consisting predominantly of equiaxed grains. The results support the contention that the ultrasonic vibrations increase the nucleation frequency in the layer of liquid adjacent to the freezing interface. CERTAIN structural characteristics of as-cast ingots are undesirable since they create considerable difficulty for subsequent processing and often produce defects in the finished product. These structural defects are illustrated in Fig. 1(a), and are: 1) planes of weakness where columnar grains growing from the different mold faces meet, 2) strength anisotropy due to the preferred orientation of the columnar grains and 3) inhomogeneity due to segregation at dendrite boundaries within the columnar grains and at the columnar grain boundaries. The type of ingot structure that eliminates 1) and 2) and diminishes 3) is the fine-grained equiaxed structure illustrated in Fig. 1(c). Many attempts have been made to produce the desirable ingot structure illustrated in Fig. 1(c) by inoculating, casting with varying superheats, vibrating or stirring, or by irradiation with ultrasonic vibrations. These attempts have met with various degrees of success, the ingots generally having the structure illustrated in Fig. 1(b). All four methods have been the subject of numerous investigations,1"4 the latter producing the most erratic behavior and inconsistent success. The method of ultrasonic irradiation during ingot solidification has shown considerable promise on small-scale ingots (diam 2 in.) but has not yet been successfully adapted to large-scale operation. The present paper considers the application of ultrasonic radiation to ingot solidification both theoretically and experimentally. The purpose of the paper is to elucidate the mechanism by which ultrasonic energy refines the ingot structure and to describe a method for producing the desirable ingot structure in both laboratory scale experiments and in ingots of commercial size. THEORY Conventional Casting—Before discussing the possible effects of ultrasonic radiation upon ingot structure let us first briefly review the reasons for the breakdown of columnar crystallization to equiaxed crystallization during ingot solidification. The following is a slightly oversimplified description. In the conventional method of casting, the alloy having a certain degree of superheat, T, is poured to fill a cold mold which is at room temperature, Tc,. Due to conduction of heat through the mold wall the outer rim of liquid metal cools rapidly to the liquidus temperature and begins to supercool. At some degree of supercooling, nuclei of solid form at random in this supercooled layer at the mold surface. The grains in this chill layer begin to grow inwards producing a solute build-up, thus lowering the freezing temperature at the interface as illustrated in Fig. 2. As growth proceeds, the temperature gradient in the solid conducts away not only the latent heat of fusion evolved during growth but it also conducts away some of the superheat of the melt so that the temperature

Jan 1, 1961

By Meguru Nagamori

DURING the smelting of the sulfide ores of copper, nickel, and certain other metals, a matte phase is formed. For a better understanding of the physico-chemical properties of mattes, binary systems such as Cu-S, Ni-S, Fe-S, and so forth, should be studied, especially in the vicinity of liquid compounds such as Cu2S, Ni3S2, FeS, and so forth. These compounds are relatively stable in the solid state although they can exhibit appreciable deviations from stoichiometry. With small deviations from stoichiometry there are large changes in the activity of both sulfur and metal this is a characteristic of both solid and liquid sul-fides near the stoichiometric compositions. In the vicinityof molten Cu2S,1 for instance, the activity of sulfur increases about 100 times for a 0.012 increase in the mole fraction of sulfur and, correspondingly, the activity of copper decreases greatly. In this sens the minor deviations from stoichiometry should be carefully taken into account in studies of such metal-sulfur melts. Metal-sulfur melts may be considered to have properties intermediate between metallic solutions and molten salts, i.e., neither entirely metallic nor entirely ionic. The radius of the ion sZ- is 1.84 as compared with 1.04? for a single bond covalent s.2 It is therefore inferred that when the sulfur is more ionic its partial molar volume is larger, although metal-metal, metal-sulfur, and sulfur-sulfur interactions may bring about further complexities. Thus, it is to be expected that the molar volumes, which are derived from density-composition relations, will help in resolving the structure of the melts. In this study the maximum bubble pressure method with bubbling gases of H2, H2S, and Ar, .was employed to measure the density. EXPERIMENTAL Materials. Silver of 99.95 pct purity was melted in an alumina crucible and hydrogen gas was then bubbled through the liquid for the deoxidation. In preparation of Cu2S, electrolytic copper powder (>99.9 pct Cu) was mixed with precipitated sulfur and heated to 1200°C in an alumina crucible under a hydrogen atmosphere. Mixtures having the approximate compositions FeS and Ni3S2 were prepared by heating reagent grade electrolytic iron or reduced nickel powder with precipitated sulfur under a hydrogen atmosphere. The H2S gas was of 98.5 pct purity, the impurities being mostly CO2 and CS2 which hardly contaminate the melts. Apparatus. The crucible system is shown schematically in Fig. 1. To minimize the variation of melt composition during a density measurement, the apparatus was designed in such a way that either Ar, H2, H2S, or mixtures of these gases could be used as the bubbling gas. When the melt had a high partial pressure of sulfur, H2S gas was used. When the partial pressure of sulfur was so low that oxygen might dissolve in the melt, the use of H2 was preferred. In intermediate cases, argon or mixtures of H2-H2S were used. Density of Dibutylphtalate. Dibutylphtalate was used as the manometer fluid. Relative to distilled water, the density of the dibutylphtalate, pdib g per cc, was measured and found to be: pdib (25°C) = 1.046 i 0.002. With the use of the temperature coefficient reported by Kemppinen and Gokcen,3 the following value was

Jan 1, 1970

By James M. Schopf

Gilbert H. Cady (Senior Geologist, Head of Coal Division Emeritus, Illinois State Geological Survey, Ur-bans)— Those coal mining and preparation engineers and operators who read this article will probably be most concerned with those parts which deal with the applied aspects of coal petrology in the fields of mining and technology. Actually the two categories overlap to such a degree that they are essentially one. The article appears to suggest that there are two points of veiw in the field of applied coal petrology. From one viewpoint the interest is in the attributes of the various macerals (Fig. 4)—vitrinite, exinite, and inertinite—-in terms of utilization (when the coal is burned, coked, gasified, hydrogenated, etc.). From the other point of view, assuming that the macerals do possess individuality in behavior, interest attaches to the possibility that coal of a particular type (maceral composition) can be prepared by discriminating methods of preparation and blending. Most of the 29 items listed for mining and technology can be assigned to one or the other of these two categories. Somewhat the same simplicity that resides in the items of the proximate chemical analysis is desirable for the petrologic analysis. This simplicity appears to be fairly well achieved by the group maceral device provided mineral matter is also included. At present, without fully adequate experimental substantiation, the three types of material represented by the group macerals vitrinite, exinite, and inertinite are regarded as sufficiently different in composition and properties so that the preponderance of any one type gives the coal distinctive properties provided it is not too high in rank. This appears to be increasingly true with coals of decreasing rank from medium volatile bituminous coals downward. The article reflects the great emphasis placed on the technique of descriptive coal petrology in America. Such description has resulted in a good understanding of the nature of the fundamental variability in the physical composition of bituminous coals. Such understanding has been attained very largely by the thin section technique used in coal bed profile analysis introduced by R. Thiessen after the manner suggested by the data assembled in Table 11. In contrast, the group maceral concept of coal analysis in terms of the categories indicated on the left hand side of Fig. 4 is particularly useful for broken coal analysis and applied coal petrology, in which evaluation is largely based on quantitative concepts. It is inadequately emphasized in this article that although the Thiessen procedure is suitable for the purpose of petrologic description in which texture and orientation are of critical importance, it is less well adapted to the technological uses of applied coal petrology. No doubt those persons whose interest may have been aroused in the possibilities of more refined coal preparation by this and other recent contributions to the literature of coal petrology will understand that certain technical aspects of coal petrology, particularly in the field of descriptive petrology, are still a matter of some controversy among the coal petrologists, but they will also appreciate that Schopf has made an important contribution to the field of coal petrology in America by pointing out that such petrology requires consideration of disoriented or broken coal samples and that results are expressed less in descriptive terms than in quantitative values with respect to the four types of material composing coal—-vitrinite, exinite, inertinite, and mineral matter. Unfortunately because so much American coal petrology has been descriptive of the coal in the bed there is a dearth of literature on applied coal petrology. Research and experimental data in this field are greatly needed.

Jan 1, 1959

By N. K. Chen, C. H. Mathewson

Recrystallization of aluminum single crystals after plastic extension is carefully studied in relation to the structure of the deformed matrix. The shapes of the new grains are analyzed with regard to slip planes and to the presence or absence of deformation bands. A mechanism by which the orientations of the grains are related to the parent lattice is described. EXPERIMENTS previously reported&apos; have been extended to develop some of the characteristics of the new crystals which are formed on annealing axially strained crystals whose deformational characteristics had been documented with special care. Thus, the presence of deformation bands affects the growth contours of the crystals, some of the strained crystals produced single crystals anew, and some, polycrystals, on annealing, while others merely "recovered" or "polygonalized" after the 600°C annealing treatment generally adopted in these tests. In the matter of orientational relationships between new crystals and the strained matrix, the present experiments have added little to previous experience, which had demonstrated great variety in the range of orientations encountered and no simple theory or correlation. For example, there has been ample evidence for the predominance in various face-centered cubic metals of a favored orientational relationship; viz., a rotation of 30° to 40° around a <1ll> axis, between grains growing in a matrix with a strong single orientation texture and the matrix itself.&apos;-&apos; This reorientation has been interpreted by various investigators in support of both the "oriented nucleation" and the "oriented growth" hypothesis. In the case of axially extended single crystals of aluminum, no general relationship, such as the one stated above, can be used to correlate the orientations of the recrystallized grains with that of the original crystal. Thus, Carpenter and Elama and Burgers and Basart7 were content to assume that the orientational relationships so developed were random in nature. Mathewson, however, in the Campbell Lecture of 1943 "rgued on the basis of <112> slip that a complex strain, chiefly characterized by rotation around a variable axis in the slip plane combined with a principal rotation around the pole of the slip plane, could be responsible for such devious relationships. Nevertheless, owing to the limited data now available dealing with orientational relationships between new grains and the single crystals strained in tension from which they have recrystallized, no adequate examination of the above generalization could be made. Here, there is the disturbing preliminary condition that any desired orientational relationship may be expressed by means of two rotations about mutually perpendicular axes, so the process lacks a certain critical flavor and any successful choice of axes meeting certain theoretical requirements could be replaced by another differently selected pair. With this reservation clearly in mind the process of double rotations, as previously indicated, was used to relate the orientations of the single crystals which grew out of the strained single crystalline matrix and was construed as certain evidence in favor of the theory of incongruent shearing action proposed by Mathewsons as a necessary element in the (111) slip process with close-packed metals. There is here

Jan 1, 1953

By John B. Myers

Vermiculite is the commercial name used to describe a micaceous mineral that expands appreciably when heated. This process, called exfoliation, results in a light weight material. The light weight material is also called vermiculite, or more exactly, expanded vermiculite. Practically all uses of vermiculite are for the expanded material. Composition and Properties Vermiculite, in its natural state, has the characteristic micaceous habit and a perfect basal cleavage and readily splits into thin laminae, which are soft, pliable, and inelastic. The monoclinic crystal faces are often marked by triangular lines at 60° and 120°. The hardness varies from 1.5 to 2 or more, depending on the composition. The specific gravity varies from 2.2 to 2.7; specific heat 0.2; fusion temperature 2,000° to 2,500°F; luster pearly to greasy; color amber, bronze, brown, dark green, and black. Feel is like talc and sometimes soapy when wet. When heated quickly at elevated temperatures, vermiculite exfoliates by expanding at right angles to the cleavage into long wormlike pieces (the name vermiculite is from the Latin vermiculari, to breed worms). This important characteristic of expansion is believed to be a mechanical separation of the layers when the contained water is converted to steam. The increase in bulk volume of commercially prepared material is 8 to 12 times, but individual flakes may expand as much as 30 times. There is no expansion parallel to the cleavage. Vermiculite may also be expanded by several chemical processes such as soaking in hydrogen peroxide, weak acids and other electrolytes. The color changes during expansion. Heat-treated material changes to a light golden bronze or cream color depending on composition. The conditions of heating affect color. Heating in an oxidizing atmosphere produces reddish colors and heating in a reducing atmosphere produces dull gray colors. The iron is generally not oxidized during chemical expansion. Vermiculite is hydrated magnesium-aluminum silicate. Although there has been much research on the chemical and structural composition, there is not yet complete agreement on the exact formula and composition. This is to be expected since vermiculite is not a mineral of fixed composition and different workers have examined different varieties. It has been proposed that vermiculite is not a single species but a family of related minerals. This has also resulted in many names for the particular vermiculite found in a certain deposit. All of this difficulty arises from the very nature of its crystal chemistry. Unlike most minerals, certain crystal structure properties and the chemical composition can be changed by the ordinary forces of nature or in the laboratory. This would suggest that vermiculite be thought of more as a variable mineral rather than a group of related species. It was stated on page 261 of this volume in the chapter on Clay Minerals by H. H. Murray of the Georgia Clay Co., that vermiculite is an equidimensional, expandable clay mineral. Gruner (ref. 14, Chap. 12) showed that the structure consists of a layer made up of two silica tetrahedral sheets with a central magnesium, iron octahedral sheet separated by two layers of water molecules and adsorbed magnesium and calcium ions. Mathieson and Walker,2a in a recent publication, agree that vermiculite must be regarded as a true clay mineral. The characteristic properties of the mineral, such as high cation ex-

Jan 1, 1960

By C. E. Reistle

All crude oils become more viscous when chilled, but the only oils that congeal and precipitate paraffin to such an extent as actually to cause production troubles are those that contain an appreciable amount of wax. In handling these oils of high wax content, three distinct problems may be encountered before the oil reaches the refinery. The first problem is the precipitation and accumulation of paraffin in the well, either in the oil string or on the face and in the pores of the sand. The second problem is the accumulation of paraffin and the congealing of oil in the transportation lines. The third problem is the precipitation of paraffin and the formation of tank bottoms. Factors That Control the Solubility of Paraffin in Crude Oil Two main factors, possibly three, govern the solubility of wax in crude oil. The first of these is temperature. The solubility of wax in crude oil increases with an increase in temperature, and as the temperature approaches the melting point, the wax becomes soluble in all proportions in the crude oil. The higher the melting point of a wax, the less soluble it is in crude oil below its melting point. All crude oils containing wax can be chilled to a point where the oil is saturated with wax. If the temperature is decreased below this point, some of the wax will crystallize from solution. Fig. 1 shows the effect of temperature on the solubility of crude paraffin in oil. The second factor is the amount of volatile constituents and gas removed from the crude oil. Evaporation of the volatile constituents and gas lessens the volume of the oil and concentrates the solution of wax in the oil; therefore less wax can be held in solution at a definite temperature. As the natural amount of wax present in the oil is constant, this results in the oil becoming saturated with wax at a higher temperature than if the volatile constituents and gas were still in the oil. As an example of this, a fresh sample of crude oil having a gravity of 39.8

Jan 1, 1928

By E. I. Larsen, E. F. Swazy, F. R. Hensel

Experience has indicated that hard bronzes are not suitable for bearing applications where high bearing loads and speeds are involved. It is the general practice to utilize softer materials for these purposes, such as copper, lead, silver, babbitt, lead-base alloys, and more recently aluminum-base alloys, preferably supported by a steel backing. It was the objective of the present investigation to study a new material produced by powder metallurgical methods susceptible to precipitation-hardening. Test MAteriaIs Preliminary tests were made with compacts containing copper, nickel and silicon in quantities sufficient to form 3 to 5 per cent nickel silicide. It mas found that this type of alloy was susceptible to the formation of a soft surface shell when sintered in tank hydrogen. The depth of the shell depended On the length of sintering time and sintering temperature, and varied in thickness from a few thousandths to as much as One eighth inch. This soft shell resulted from the preferential oxidation of silicon, thereby reducing the efficiency of age-hardening by the nickel silicide compound. The body of the sintered compacts below the soft shell could be precipitation-hardened to a hardness of 70 to 85 Rockwell B, by quenching from goo°C. and age-hardening at 450°C. A series of tests was made with various addition agents, in order to decrease the rate of preferential oxidation, and it was found that phosphorus was most beneficial in this respect. After considerable experimentation, the following nominal com-position was accepted as standard: 2.4 per cent nickel; 0.8 silicon; 0.3 phosphorus; balance copper. The physical propertties and certain bearing properties of this alloy are described in the present paper Preparation of Compacts Several methods of incorporating the hardening ingredient (nickel silicide) were studied. Compacts formed from copper, nickel and silicon powders were found to be inferior to those fabricated from prealloyed nickel silicide master alloys, because of the rapid oxidation of pure silicon during sintering. The use of a prealloyed nickel silicide hardener containing 25 per cent silicon and 75 per cent nickel could be further improved by preparing a master alloy, incorporating nickel, silicon, phosphorus and copper, having the following nominal composition~ 25 per cent nickel; 7 silicon; 3 phosphorus 64 copper. This alloy is brittle in the cast condition and can be readily powdered. Sintering Procedure The blended powders were pressed at &apos;5 to 40 tons per sq&apos; in., the pressure depending on the size and shape of the compacts. Sintering was carried out in hydrogen or cracked ammonia atmospheres at

Jan 1, 1946