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By S. Storchheim

MORE and more attention is being paid to the bonding of metals in their solid states. For a better understanding of this technique for joining metals and how it is affected by changes in temperature, pressure, and time at temperature and pressure, a detailed report concerning nickel to aluminum bonding has been published.' In order to broaden the knowledge accrued, some additional work concerning solid state joining of aluminum to copper and aluminum to zirconium was performed. The investigation of the Al-Cu system was considerably more extensive than the investigation of the Al-Zr system. For the A1-Cu system, not only were tensile sudies made but intermetallic penetration rate investigations also were carried out. The effect of temperature on intermetallic penetration rate for the A1-Cu system was determined at 11 tsi pressure, held 2 min. Procedure Apparatus: The hot pressing technique was the means of solid state reaction used and required the equipment depicted in Fig. 1. The following procedure was involved: The two metals to be reacted were placed in an aquadag-lubricated 18-4-1 tool steel die, 16 in. high by 1.440 in. ID, between punches of 1.366 in. diam made of the same material. A thermocouple well was located in the die body 3½ in. down from the top of the die, while another well was located centrally in the bottom punch 8½ in. from the bottom of the die. This die assembly was located in three cylindrical ceramic heating furnaces placed in tandem. Each furnace was controlled individually by a Variac power transformer. In turn, the die and furnaces were placed in a water-cooled stainless steel pot which could be evacuated. A cover, which contained a centrally located Wilson seal with an 18-4-1 1 in. diam ram running through it, was bolted on the pot. After sealing, the pot was evacuated by a roughing pump to 200 microns pressure, after which a diffusion pump was used to bring the pressure down to 5 to 15 u. At this pressure, the furnaces were turned on. As soon as they started to heat, out-gassing of the entire unit raised the pressure to 30 to 400 p. By the time the specimens were at temperature ready to be pressed, approximately 4/2 hr, the vacuum pumps had re-established the 5 to 15 u pressure. Once the desired temperature was reached, the required pressure was applied for a predetermined length of time to the 1 in. ram, through to the top punch, and to the specimen. When the time for keeping the specimen under pressure had elapsed, the pressure was released, the energizing coil current turned off, and the assembly allowed to cool. After cooling, the die was removed from the pot and the specimen was ejected. Specimen Preparation: Two different types of specimens were made for this investigation. One was for subsequent tensile testing, while the other was for determination of intermetallic alloy zone penetration into the parent metals. Tensile Bars—Commercially rolled copper pieces in. thick or zirconium sheet pieces 1/32 in. thick and 1.366 in. diam were placed between commercial 2-S aluminum rod 1 in. thick and 1.366 in. diam. This sandwich in turn was slipped into a 2-S aluminum sleeve 1.438 in. OD and 1.370 in. ID. This sleeve lined the couple up and prevented the aquadag lubricant from getting in between either the A1-Cu or Al-Zr interfaces. Immediately prior to the specimen assembly, the copper or zirconium was abraded on the flat surfaces with 320 grit silicon carbide paper, producing clean smooth surfaces. The aluminum was chemically cleaned just before assembly by: l—degrease in acetone, 2—distilled water rinse, 3—immersion for 3 min in 5 pct NaOH at 70" to 80°C, 4—distilled water rinse, 5—immersion for 2 min in 50 pct HNO3 solution at room temperature, 6—distilled water rinse, and 7—drying in a blast of gas. After the A1-Cu sandwiches were hot pressed and ejected, the specimens were machined such that the aluminum sleeve was removed, and the remaining aluminum was then threaded; the bar so produced was tested later for tensile strength. In all the instances where Al-Cu couples were tested, the specimens broke during the test at the Cu-A1 interface and never within the aluminum or copper. The ultimate tensile strength values at times showed considerable scatter for a set of given reaction conditions. Because of this, as many as three to five specimens were made for a particular set of conditions. The trend of the average tensile strengths obtained was not as conclusive as was the trend of the maximum tensile strengths, the latter values being obtained under optimum reaction conditions. Therefore, the values of ultimate tensile strength given herein are maximums.

Jan 1, 1956

By A. E. Bibb, J. R. Fascia

Single-crystal wafers of zirconium have been exposed to 680°F neutral water. The single crystals were of known orientation and weight-gain data as a function of crystal orientation were obtained. These data show that all the crystal faces studied obeyed a cubic rate law out to the time of transition whereupon the crystals corroded at an approximately linear rate. The time to transition varied from 114 days for (1074) crystals to about 325 days for the (2130) faces. The epitaxial relationship be-tween metal and monoclinic oxide was found to be (0001) H (111) and [1120] 11 [101]. A black tight adherent oxide layer was formed on the crystals in the pretransition range. This black oxide was found to be monocrystalline. The white corrosion product produced after transition was found to be polycrys-talline but highly oriented. X-ray line-broadening studies found that the black oxide was a highly strained structure whereas the white oxide was relatively strain-free. These results indicate a strain-induced re crystallization or fragmentation accompanies the change from protective black oxide to nonprotective white oxide. ZIRCONIUM alloys have been used quite extensively in high-temperature aqueous environments. Alloy additions can be made to commercial sponge zirconium which enhance the corrosion resistance of the zirconium in both water and steam media, which raise the tolerance limit for certain impurities detrimental to corrosion resistance, and which reduce the amount of free hydrogen pickup during corrosion. The development of the corrosion-resistant zirconium alloys has been a long and tedious job involving trial and error methods. This technique has been necessary because of a lack of fundamental data and hence understanding of the corrosion mechanisms. The objective of the work described herein was to provide some fundamental data with respect to the aqueous corrosion of zirconium crystals as a function of the orientation of the exposed surfaces. Hg. The zirconium chunk was then cooled to below the transformation temperature (862°C) and reheated to 1200°C for 8 hr. The ultimate size of the zirconium grains increased with the number of cycles. Rapid or even furnace cooling through the transformation temperature produces a considerable amount of substructure which was intolerable in corrosion experiments as it would be in the study of any crystallographically dependent property. It was found that a high-temperature a-phase anneal for approximately 4 days reduced the substructure below the limits detectable by visual or X-ray means. Crystals so produced were carefully cut from the massive zirconium chunk and oriented by standard back-reflection Laue techniques. The crystals were then mounted in a goniometer head and, by using the three degrees of freedom available, slices on the order of 0.015 to 0.020 in. were cut parallel to any desired crystal plane. These slices were then carefully polished on both sides to produce smooth flat faces, pickled to remove about 0.002 in. per face, annealed for 1/2 hr at '750°C in a vacuum of approximately 10"5 mm Hg, flash pickled, and checked for orientation. The pickling solution was 45-45-10 vol pct HN0,-H20-HF and continuous agitation was provided to eliminate pitting of the slices. Any slice that was not within 2 deg of the desired orientation was discarded, and any evidence of substructure as indicated by the Laue spots was also grounds for discarding the sample. Thin slices were used for the corrosion tests because weight gain per area data could be obtained with only a minimum area exposed to the corrosive media that was not of the desired orientation. The thin single-crystal slices were of irregular shape and as a result the areas were determined by placing a crystal inside an inscribed square of known area, enlarging a picture of this assembly about X5, and tracing both the enlarged square and crystal with a planimeter. The zirconium used to produce these single crystals was crystal-bar grade, a typical analysis of which is given in Table I. An oxygen analysis on prepared crystals gave a concentration of 205 ppm. The hydrogen concentrations are believed to be less than 15 ppm due to the dynamic vacuum anneal given each crystal. Typical nitrogen values for zirconium treated in this manner are about 10 to 20 ppm. RESULTS AND DISCUSSION Single-crystal wafers have been exposed to de-oxygenated, deionized water in static autoclaves.

Jan 1, 1964

By R. Schuhmann, J. Th. Overbeek, P. L. De Bruyn

THE technique of concentrating valuable minerals from lean ores by flotation depends upon the creation of a finite contact angle at the three-phase contact, mineral-water-air. If the mineral is completely wetted by the water phase, contact angle zero, there is no tendency for air bubbles to attach themselves to the mineral. However, when the contact angle is finite, the surface free energy of the system, water-air bubble-mineral particle, can be diminished by contact between the bubble and the particle, and if not too heavy the mineral will be levitated in the froth. With a few exceptions, all clean minerals are completely wetted by pure water. Thus the art of flotation consists in adding substances to the water to make a finite contact angle with the mineral to be floated, but to leave the other minerals with a zero contact angle. The contact angle concept and experimental measurements of contact angles have played important roles in flotation research for several decades.'-" Nevertheless, there remain unanswered some basic questions as to the scientific significance of the contact angle and the nature of the processes by which flotation reagents affect contact angles. The contact angle is a complex quantity because the properties of three different phases, or rather of three different interfaces, control its magnitude. Considering the interfaces close to the region of ternary contact to be plane, the relation among the contact angle and the three binary interfacial tensions is easily derived. The condition for equilibrium among the three surface tensions, Fig. 1, or the requirement of minimum total surface free energy leads to Young's equation, Eq. I: ysa — ysl = yLA cos 0 [1] According to this equation, the contact angle has one well-defined value. Actually it is found in many experiments that the value of the contact angle depends on whether the air is replacing liquid over the solid (receding angle) or the liquid is replacing air (advancing angle). The receding angle is always the smaller of the two.4 Two explanations have been offered for this experimental fact. According to some investigators,5-8 roughness of the surface causes apparent contact angles that are different for the receding and the advancing cases although the actual local contact angle may be completely determined by Eq. 1. The other explanation involves the hypothesis that the solid-air interface after the liquid has just receded is different from the same interface when no liquid has previously covered it.1,4 Adsorption of constituents of the air or liquid might play a role here. In this discussion the difference between advancing and receding contact angle will be neglected and plane surfaces where Eq. 1 describes the situation will be considered. But there is still a fundamental obstacle to the application of Young's equation. The surface tension of the liquid (rla) can easily be determined, but the two surface tensions of the solid (rsa and ySL) cannot be measured directly. Eq. 1, however, is not without value. By contact angle measurements it is possible to establish how ysl — ysl varies with the addition of solutes to the liquid phase. Also, Eq. 1 affords a convenient starting point for calculating net forces and energy changes involved in the process of bubble-particle attachment.1,2 . If for the moment surface tension of the liquid (yLa) is considered a constant, an increase in ysa — ysL, will tend to decrease the contact angle. A decrease in ySA — ysl, corresponds to an increase of the contact angle. In cases where ySA — ySL > yLa the contact angle is zero; it will only reach finite values when ysa — ysa has been decreased below YLA. Thus on the basis of Young's equation and contact angle measurements alone, it can be learned how flotation reagents affect the difference Ysa — ysl, but no conclusions can be drawn as to the effects of reagents on the individual surface tensions ysa, and ysL, not even as to signs or directions of the surface tension changes resulting from reagent additions. A quantitative relationship between the surface tension or interfacial tension and the adsorption occurring at a surface or an interface is given by the Gibbs equation, which for constant temperature and pressure reads dy = — 2 T, du, [2] where dy is the infinitesimal change in surface tension accompanying a change in chemical potential

Jan 1, 1955

By Charles H. Jacoby, Stanley J. LeFond

Salt, or halite, has a long and most varied history. While we know the Chinese were producing salt as early as 3000 B.C., the first written reference to salt appears in the book of Job recorded about 2250 B.C., which reads: "Can nothing which is unsavory be eaten without salt?" We do not know when man first used or realized that he needed salt. Perhaps one of our early Eolithic ancestors noted a piece of salt shining along the shore of a salt lake or a bay. He may have been attracted by its shining luster and tasted it. He found that it had a tart, zesty, distinctive flavor and perhaps chewing a large piece, became ill. However, by experimentation he soon learned that taken in the proper proportions salt was a very pleasant additive to his food. He may have noticed, too, that it increased his feeling of well-being. Thus, when the curtain of recorded history rises, we find man using salt for his health's sake, seasoning his food with it, feeding it to his animals, and using it in many superstitious and religious ceremonies. These uses, however, are a far cry from the uses for salt today. The first attempts of white man to make salt in continental United States were reported in the year 1614, while the first commercial production was in 1753 from the Kanawha licks. Practically all this salt was for human consumption, preserving food, and curing hides. Prior to the coming of the white man, Indians are known to have made salt from salt springs such as those that existed at Avery Island, LA, Charleston, WV, Saltville, VA, and Onondaga, NY. In 1862 the first rock salt was mined in the US from the Avery Island salt dome. Almost immediately thereafter, rock salt was mined at Saltville, VA and then at Retsof, NY in 1885. Of the more than 39 million tons produced annually in the United States, about 58% or 23 million tons are consumed by the chemical industry in the production of chlorine, caustic soda, hydrochloric acid, sodium metal, and some 30 other basic chemicals. These basic chemicals, in turn, are used in the preparation of approximately 14,000 chemicals which range from soap and detergents, to such chlorinated hydrocarbons as DDT, BHC, carbon tetrachloride, etc. Utilization of cavities created in salt beds and domes has grown rapidly since 1947 until now the waste salt is creating an ecological problem. The uses for both dry- and solution-mined cavities range from the storage of liquid hydrocarbons to containerized storage of toxic wastes, from compressed air for the peak shaving of power to storage of nuclear wastes. Geology Mineralogy Properties: Because of its simple structure, halite, the mineralogical name for salt, was the first structure to be analyzed by X-rays. It has the following properties: Formula: NaCl (Na-39.34%. Cl2-60.66% ) Crystallography: isometric, hexoctahedral, 4/m 32/m Space group: Fm3m A0: 5.627 kX Cell contents: Na4CI4 Habit: usually cubic, rarely octahedral, massive, granular to compact Physical properties: Refractive index: 1.554 Twinning: observed on {111} Cleavage: {001} perfect Fracture: conchoidal, brittle

Jan 1, 1983

By G. Meyrick, H. W. Paxton

Observations on the tensile deformation of single crystals of austenitic stainless steels as a function of composition, orientation, and temperature are described and compared with relevant data for other alloys. Crystals free from second phases show sharp yield points followed by Lüders' extensions of up to 20 pct. The critical resolved shear stress is strongly temperature-dependent increasing fourfold between 423O and 77°K. A temperature-independent low rate of hardening follows the Luders' extension and is frequently associated with overshoot. Unlike pure metals where Proficse cross slip usually occurs at the end of linear hardening, this stage is terminated either by cross slip or by slip on the conjugate system, the particular node apparently depending upon initial orientation and composition. The presence of 6 ferrite or martensite has a profound effect upon the magnitude of the yield stress and the shape of the stress-strain curve. In experiments on transgranular-stress corrosion cracking of austenitic stainless steels in boiling magnesium chloride, several workers1'2 have shown that increasing amounts of nickel tend to reduce the probability of specimen failure. Reed and paxton3 have observed in single crystals that the macroscopic crack plane changes as the nickel content is increased. For 18 pct Cr-8 pct Ni, the crack plane is sensibly perpendicular to the applied tensile stress; for 20 pct Cr-20 pct Ni the crack plane is (100). The average crack-propagation speed is much lower in the 20 pct Ni crystals. Furthermore, the possible importance of stack-ing-fault energy in nucleation and growth of cracks has been suggested by a number of workers. While the general effect of variations in stack ing-fault energy appears to be quite well-correlated with observed variations in cracking characteristics, each of the theories assigns rather different detailed reasons for these effects. Because the stack ing-fault energy of austenitic steels is believed to be increased with increasing nickel content, and because some theories of trans-granular cracking postulate a mechanical stage in the crack propagation (rather than relying entirely on electrochemical solution), it appeared to be of some interest to investigate the mechanical properties of a series of different compositions of aus-tenite single crystals. These experiments were considered of intrinsic value in view of the relative scarcity of such data on fcc alloys. This paper gives the results of some experiments carried out with this aim in mind, and suggests various 'other experiments which may be helpful in future studies. The experiments are also of interest in view of the recent interest in obtaining higher-strength steels by control of the imperfection content of austenite; although the compositions are not directly comparable, the results are still probably valuable. Comparisons with experiments on other fcc alloy crystals are made where possible to see how well the general pattern of behavior is understood. EXPERIMENTAL PROCEDURE The alloys used in this investigation were vacuum-melted heats of nominally 20 pet Cr-20 pet Ni-60 pet Fe, 20pctCr-16 pct Ni-64 pct Fe, and 20 pctCr-12 pet Ni-68 pet Fe.* Analyses of the material are

Jan 1, 1964

By D. H. Desy, L. C. Fincher

The magnesium-rich end of the Mg-Ti phase diagram was investigated. The liquidus, solidus, and solvus boundaries to 1 pct Ti were established. All alloys were prepared by saturating molten magnesium with titanium in a consumable titanium crucible under inert gas maintained at 230 psig. The liquidus of the Mg- Ti system was determined by analysis of dip samples taken from 700° to 1300°C under equilibrium conditions in a pressurized inert atmosphere furnace and by analysis of small ingots rapidly poured and quenched from 1400° to 1500°C. The solubility of titanium in magnesium ranged from 0.018 wt pet Ti at 700°C (0.012 wt pet at 650°C by extrapolation) to 1.035 wt pet Ti at 1500°C. The solidus for compositions ranging from 0.03 to 1.00 wt pet Ti was determined to be 650° ± 1°C by thermal analysis. The titanium solid solubility values ranged from 0.08 wt pet at 350°C to 0.19 wt pet by extrapolation to 650°C. The freezing reaction is peritectic. No intermetallic compounds were found in the system; the phase in equilibrium with molten magnesium saturated with titanium was found to be titanium with magnesium in solid solution. Solid titanium will dissolve at least 1.32 wt pct Mg. PREVIOUS investigations of the Mg-Ti system have shown considerable disagreement on the solubility of titanium in liquid magnesium. Furthermore, the solid solubility of titanium in magnesium has not been well established. Liquidus curves for previous work and for the present investigation are shown in Fig. 1. Aust and Pidgeon1 used a dip-sampling method on molten magnesium held in equilibrium with solid titanium under a protective atmosphere to determine the solubility and found that it ranged from 0.0025 wt pet Ti at 651°C to 0.015 wt pet Ti at 850°C. Eisenreich2 introduced titanium into molten magnesium by means of TiCL4 adsorbed on BaCl2. Ingots were then cast at various temperatures. Making the assumption that only the titanium dissolved in magnesium at the time of casting was soluble in H2SO4, Eisenreich determined the solubility of titanium in molten magnesium to range from 0.003 wt pet at 655°C to 0.115 wt pet at 800°C. Eisenreich also determined the solid solubility of titanium in magnesium to be 0.015 wt pet at room temperature and 0.045 wt pet at 500°C. Since the solid solubility just below the freezing temperature for the bulk of the alloy was much larger than the liquid solubility just above the freezing temperature, Eisenreich concluded that the freezing reaction was peritectic. Obinata et al.3 equilibrated molten magnesium with titanium in hermetically sealed titanium containers which were then furnace-cooled. The titanium content of the magnesium was then determined and found to range from 0.170 wt pet at 700°C to 0.85 wt pet at 1200°C. No intermetallic compound was found in the system. The Armour Research Foundation4 determined two points on the solvus by electrical resistivity methods: 0.00057 wt pet at 200°C and 0.0008 wt pet at 300°C. At higher temperatures, data were meaningless with no trends observable. The authors of this report believed that the lack of significant data at the higher temperatures was due to variations in specimen geometry, although there was no positive evidence to verify this supposition. The present investigation was undertaken to clarify the uncertainty in both the liquidus and solvus of the magnesium-rich end of the Mg-Ti system. EQUIPMENT AND MATERIALS The equipment used in this investigation, with some modifications, was essentially that used by Crosby and Fowler5 in their determination of part of the Mg-Zr phase diagram. The equipment, as modified for this work, is shown in Fig. 2. It consists of a sealed furnace chamber which can be pressurized with inert gas so that melts can be made above the boiling point of magnesium at atmospheric pressure. Melts are made by induction heating in a titanium crucible which, after diffusion of sufficient magnesium into the walls of the crucible to saturate the titanium at the sampling temperature, comprises the solid phase in equilibrium with the molten magnesium. Dip samples may be taken with the sampling tube, or the entire furnace may be tilted so that ingots may be poured into a mold in the side chamber. The principal difference from the earlier apparatus is in the thermocouple, which in the present equipment is enclosed in a protection tube and immersed directly in the melt. The tips of both the thermocouple protection tube and the sampling tube, which dip into the melt, are made of high-purity titanium. The 4 1/2-in.-long titanium tip of the sampling tube is threaded into a steel tube, O in Fig. 2, which extends through the top of the furnace. To determine whether the temperature at the tip of

Jan 1, 1969

By C. H. Brehaut, W. N. Taylor, R. S. Douglas, H. A. Shannon

The name for this new method of mining is derived from a composition of Horizontal, Radial, Diamond, and the drilling is from raises. This method, worked out at Copper Mountain, B.C., is believed to be distinct in many features from other known methods. Geology The ore deposits of copper Mountain are related to the copper Mountain stock, which is an ideal example of the magmatic in in that it grades from a basic gabbro at the border to an almost pure orthoclase-pegmatite core. The "contact" ore bodies lie along the contact of the gabbro and an older complex of volcanies and sediment termed the "Wolfe Creek" formation. These older rocks, collectively referred to as greenstone, had been fractured prior to the intrusion of the stock and were highly metamorphosed during the intrusion. The "outlying" ore bodies are somewhat different in character, though a similar structural pattern prevails. It is believed that a deep-seated magma of which the Copper Mountain stock is a part has given off solutions that caused a partial graniti-zation of some of the volcanies. Mining problems are caused further by the presence of a series of soft barren dikes intersecting a great many of the ore bodies, which are about 30 ft. wide, strike north-south, and dip at a high angle to the east; and are further increased by the presence of four major faults, with a great many minor faults running at acute angles from them. Fault zones average 8 ft. in width, and consist of gouge and breccia. They strike northeast and dip steeply to the northwest. The faults cut through the ore zones and the dikes, and continue on into the gabbro. The general mine structure with two types of Ore bodies, bounded by weak walls and intersected by several series of soft barren dikes and major faults, indicated that a method of mining should be devised that would remove the ore at low cost with the least disturbance of the waste walls and dikes. , Theoretical Estimate of Stoping with the Diamond Drill After consideration of various methods, the most suitable one appeared to be horizontal drilling to break the ore in a manner similar to shrinkage stoping Drilling vertical holes or rings from a bench and breaking to an open slot was eliminated because the weak walls of ore, dike or waste would not permit this type of opening. It was then decided to drill either horizontal radial holes from a raise or parallel holes from a slot cut across the ore body. After discussion, the latter method was believed unsuitable, for the following reasons:

Jan 1, 1946

By Edmund M. Warner

Any city dweller who has walked alone along a remote mine passageway has to be impressed by the eerie silence-the total absence of noise except for one's own breathing and scuffing of boots on the bottom. An underpound mine can have tremendous contrasts, from complete silence to the ear piercing clatter of percussion drills working in the mine roof. Noise in underground mining machines is both useful and detrimental. Without characteristic noises that are recognizable to miners, operators would have a more difficult job operating their machines. Noise serves as a warning of approaching machinery, and changes in noise give indication that breakdowns may occur. But excessive noise is a health hazard. In recognition of this fact, our congress included noise exposure as a part of the "Coal Mine Health and Safety Act of 1969." As [Fig. 1] indicates, allowable noise exposure is established by specifying a time duration permitted at different noise levels. This is the well known "Walsh-Healey" criteria which govern noise exposure in many industries. In most industries noise exposure is not a constant value. Noise emitted from coal mining machinery varies widely, and therefore interpretation of compliance is not a simple matter. Time, environment, instrumentation and machine productivity, as well as the designed machine characteristics affect the results. It is the purpose of this paper to present the underground coal face machinery noise problem from a manufacturer's point of view. Manufacturers are very much aware of their responsibility to alleviate the noise problem. Not infrequently, orders are received from coal operators that a given new machine must comply with "The Coal Mine Health & Safety Act" noise regulations. Such a request is indicative of the misunderstanding which exists with machine users, while indicating their desire to comply with the law. Obviously, if all machinery could be designed and used at some arbitrary low noise level, it would be possible to simplify the regulations. However, there still remains the pervasive problem of existing machines. Extensive investigation to create practical retrofit kits for existing machines, to substantially reduce noise have been only marginally successful. Certain machine mechanisms are inherent noise makers. The only really good solution is to substitute a quieter mechanism. Such overall new designs have been undertaken, and several examples are mentioned later in this paper. Before describing machine noise problems, it is necessary to define noise values. Noise levels are measured in decibels. The designation "DBA" is decibels measured on the "A" scale, or one in which the frequency sensitivity of the instrumentation is about the same as the human ear. The numbers are often misinterpreted because it is a logarithmic, rather than an arithmetic scale. In comprehending the numbers, it should be remembered that any increase of 3 dB doubles the sound power. In practical terms this means that two noises of equal power at the same distance away increases a dB reading by three. Consider [Fig. 2] showing a simplified case of a worker on a machine subject to

Jan 1, 1980

By R. F. Mehl, C. S. Barrett, A. H. Geisler

THE studies of the mechanism of precipitation and of the resulting property changes in aluminum-silver alloys1-3 have presented some new concepts of the aging reaction-concepts that may be fundamental in establishing a complete quantitative theory of age-hardening. With both aluminum-copper and aluminum-silver alloys, thin platelike aggregates form parallel to the Widmanstätten planes of precipitation.1,4 These platelets grow in lateral dimensions and in thickness with aging time until they are thick enough to produce an X-ray diffraction line pattern. Their structure is that of a transition lattice which is coherent with the matrix, since the atomic spacings in the matrix and the precipitate are the same on each side of their common interface.2,4 The equilibrium precipitate forms later from and at the expense of the transition lattice. Since age-hardening occurs during the formation and growth of the transition lattice, the major contributor to the hardening no doubt is the stress condition in the matrix resulting from the matrix holding the precipitate in the coherent condition. The development of these stresses also appears to be responsible for an increase in the electrical resistance superimposed on the normal decrease resulting from a change in the concentration of the matrix during aging.3 The two consecutive reactions constituting the aging process are accompanied by characteristic microstructural alterations. The initial precipitation process results in the formation of a Widmanstätten figure, while the later transformation of the transition lattice to the equilibrium lattice is accompanied by a coalescence, in the case of aluminum-copper alloys,5 and by the appearance of light areas at the grain boundaries with aluminum-silver alloys showing a structural rearrangement of matrix and precipitate.3 This latter reaction is similar microscopically to the so-called "discontinuous precipitation." Possibly discontinuous precipitation is a process that often if not always follows true precipitation of a coherent lattice and during which the transformation of the coherent transition lattice to the equilibrium lattice takes place accompanied by matrix recrystallization.3 EXPERIMENTAL PROCEDURE The alloys were made using 99.97 per cent Al or distilled magnesium, with

Jan 1, 1943

By C. H. Brehaut, W. N. Taylor, R. S. Douglas, H. A. Shannon

THE name for this new method of mining is derived from a composition of Horizontal, Radial, Diamond, and the drilling is from raises. This method, worked out at Copper Mountain, B.C., is believed to be distinct in many features from other known methods. GEOLOGY The ore deposits of Copper Mountain are related to the Copper Mountain stock, which is an ideal example of the magmatic differentiation in that it grades from a basic gabbro at the border to an almost pure orthoclase-pegmatite core. The "contact" ore bodies lie along the contact of the gabbro and an older complex of volcanics and sediment termed the "Wolfe Creek" formation. These older rocks, collectively referred to as greenstone, had been fractured prior to the intrusion of the stock and were highly metamorphosed during the intrusion. The "outlying" ore bodies are somewhat different in character, though a similar structural pattern prevails. It is believed that a deep-seated magma of which the Copper Mountain stock is a part has given off solutions that caused a partial granitization of some of the volcanics. Mining problems are caused further by the presence of a series of soft barren dikes intersecting a great many of the ore bodies, which are about 30 ft. wide, strike north-south, and dip at a high angle to the east; and are further increased by the presence of four major faults, with a great many minor faults running at acute angles from them. Fault zones average 8 ft. in width, and consist of gouge and breccia. They strike northeast and dip steeply to the northwest. The faults cut through the ore zones and the dikes, and continue on into the gabbro. The general mine structure with two types of ore bodies, bounded by weak walls and intersected by several series of soft barren dikes and major faults, indicated that a method of mining should be devised that would remove the ore at low cost with the least disturbance of the waste walls and dikes. THEORETICAL ESTIMATE OF STOPING WITH THE DIAMOND DRILL After consideration of various methods, the most suitable one appeared to be horizontal drilling to break the ore in a manner similar to shrinkage stoping. Drilling vertical holes or rings from a bench and breaking to an open slot was eliminated because the weak walls of ore, dike or waste would not permit this type of opening. It was then decided to drill either horizontal radial holes from a raise or parallel holes from a slot cut across the ore body. After discussion, the latter method was believed unsuitable, for the following reasons:

Jan 1, 1945

By P. D. Zemany, G. W. Sear, B. W. Roberts

Vanadium metal is embrittled by hydrogen at a temperature as low as 250°C when held in the presence of manganese metal and water vapor in a rough vacuum. It is established that the property changes are caused by the catalytic decomposition of water vapor at the vanadium surface and the diffusion into and solution in the vanadium of the resultant hydrogen. It is found that manganese is a necessary component of the catalyst. The manganese is transported in the vapor phase by an unknown molecule. A deuterium tracer experiment demonstates the role of water vapor in the embrittle-ment process. VANADIUM metal foils were observed to become embrittled' at a temperature of about 300 °C when held in the presence of manganese metal and a small amount of moist air, This paper describes the investigation to find the embrittling agent and an understanding of the relatively low temperature reactions that are involved. Experimental The vanadium metal foil used was prepared by cold-rolling and pack-rolling 32 mil sheet" in a series of steps down to 1 mil foil. The original observation was confirmed by sealing vanadium foils of 3 x 10 sq cm into individual Pyrex tubes with manganese powder† and a con- trol tube containing only the vanadium foil. These tubes were evacuated to 10 -5 mm Hg without baking and sealed. After heat treatment for 200 hr at 300°C, the control foil showed no change in duetility, whereas the foil contained in the manganese— containing tube was embrittled. The visual appearance of each was unchanged. A series of Pyrex sample tubes, about 2.5 cm diam and 25 cm long, were prepared, each containing a 3 x 10 sq cm piece of foil and 5 g manganese powder at the lower end of the tube. By reducing the time of anneal and the temperature of these samples, it was found that embrittlement could be created at 250°C in a time as short as 1 hr. Since the vanadium metal used here has been drastically cold-worked by rolling, it is assumed that it contains a maximum number of dislocations. To check the possible necessity of dislocations in this low temperature reaction, a vanadium foil sample was annealed in Vycor for 2 hr at 800°C to re crystallize and reduce the dislocation concentration. Metallographic examination showed grains which were not visible before annealing. The embrittlement procedure was carried out at 300°C and 3 hr. Upon checking the foil no embrittlement was observed. Further experiments demonstrated that about 6 hr at 300°C are required to create embrittlement in the foil. This delay in the onset of embrittlement in the vanadium foil suggests but does not prove that dislocation channels play a role in the embrittlement phenomena. If manganese metal is necessary for this low temperature embrittlement, do other elements in the transition metals group yield the same result? To check this qualitatively, a group of elements of similar atomic radii were obtained and sealed as before into Pyrex tubes with a sheet of vanadium foil. These tubes were annealed at 250°C for 6 hr and included (with radii)-2 A1 (1.4A), As (1.25A), Be (1.2A), Co (1.25A), Cr (1.45A), Cu (1.25A), Fe (1.25A), Ga (1.2A), Ge (1.25L%), Mn (1.3A), Ni (1.25A), Si (1.2A), Ti (1.45A), Zn (1.3A), air, H,O, 10 cm Hg of dry hydrogen, and MnO, powder. Upon testing the above sample foils for brittleness, only the manganese-containing tube yielded a brittle foil. Manganese Transport—To eliminate contact of manganese metal powder and vanadium foil, sample tubes were prepared with fritted glass barriers. The embrittlement reaction was still found to occur. Thus, the mode of transfer of manganese is certainly vapor transport. A vanadium foil was embrittled by this mechanism in an evacuated Pyrex tube for 8 hr at 300°C. By means of X-ray fluorescence analysis,' the amount of manganese added to the surface was established at 5 ±2 x 10 -6 g per sq cm. Since the average rate of manganese deposition is known, an effective average pressure of an assumed carrier compound can be computed. ___ P = M/T v2p mkT

Jan 1, 1959

By C. S. Smith

The solubility of tantalum at 1100°C is 0.025 pct in pure copper, 1.2 pct with 20 pct Ni, and 2.7 pct with -30 pct Ni. The solubility decreases with temperature, and the alloys are precipitation hardenable. A 79/20/1 Cu-Ni-Ta alloy reaches maximum hardness after aging at about 750°C and, if cold worked, does not recrystal-lize below that temperature. The alloys have good tensile properties at moderately elevated temperatures and, since they can be hot and cold worked nearly as easily as cupronickel, they are suggested for service at temperatures above the usual limits for copper alloys. MASSIVE tantalum dissolves extremely slowly in copper-rich alloys, and tantalum powder forms refractory surface layers which prevent its solution unless special precautions are taken. After many trials, an 80 pit recovery was consistently obtained by using a mixture of a finely divided tantalum powder with two or three times its volume of potassium tantalum fluoride (K2TaF1,-melting point about 750°C) poured in a slow stream directly on to the surface of the molten copper alloy, so that each particle would remain coated with flux and be immediately and individually wetted by the molten metal. A 50-50 nickel-tantalum alloy has a melting point of about 1400°C and small lumps of it slowly but satisfactorily dissolve in molten copper-nickel alloys as does commerical "ferro-tantalum." The high affinity of tantalum for carbon makes it necessary to avoid carbonaceous crucibles. COPPER-TANTALUM ALLOYS Castings with good shrinkage resulted when 0.1 pct Ta or more was added to copper melted under charcoal and cast in air. Copper in two-pound melts to which 0.1, 0.15, and 0.2 pct Ta had been added retained residual amounts, by analysis, of 0.025, 0.023 and 0.026 pct, respectively. The solubility of tantalum in molten copper at about 1200 °C is therefore about 0.025 pct. The electrical conductivity of these three samples was 100.48, 100.00 and 100.20 pct IACS in the annealed condition, and 98.24, 97.98 and 98.08 in the cold-drawn condition. Wires 0.080 in. in diam withstood from thirteen to nineteen reversed bends after annealing for 30 min in hydrogen at 850°C and the metal was therefore completely deoxidized. The annealing temperature corresponding to 50 pct loss of work hardness in 1 hr in a strip cold rolled 77 pct reduction was 175C, compared to 230°C for equivalent undeoxidized material. It is unusual for a decrease of recrystallization temperature to result from an alloying addition, and the tantalum probably combines with and removes some minor impurity in the original copper that restrained its recrystalliza- tion. No difficulty whatever was encountered in hot or cold rolling or drawing these ingots, and were tantalum not so expensive it would make an excellent deoxidizer for copper. COPPER-NIcKEL-TANTALUM ALLOYS Studies were made of the solubility of tantalum in a large number of copper-rich alloys, but of these significant solubilities were found only in the case of an iron alloy (which, however, separated into two immiscible liquid layers) and alloys of copper and nickel, in which tantalum is freely soluble and which were found to have interesting properties. The latter alloys are the subject of U. S. Patent No. 2,430,306 (1947). They are not at present available commercially. The Ternary Constitution Diagram—The copper-rich corner of the constitution diagram was constructed on the basis of microscopic examination of samples of various composition and treatments. The alloys were hot rolled to 0.25 in. from castings 0.625 in. thick, then annealed for 1 hr at 1000°C, quenched, cold rolled to 0.10 in. and finally annealed for various periods of time at temperatures between 800" and 1100°C in a nonoxidizing atmosphere and quenched. When the solid-solubility limit had been transgressed, particles of a compound believed to be Ni2Ta*were

Jan 1, 1960

By R. C. Hassinger, D. V. von Rosenberg

Transverse dispersion has received considerably less treatment in the literature than has longitudinal dispersion. Different methods for determining transverse dispersion coefficients have been used in different investigations, and the results obtained have not been consistent enough to permit accurate generalizations as to the effect of various physical parameters on the magnitude of these coefficients. A numerical solution to the differential equation describing transverse dispersion in the absence of longitudinal dispersion was obtained to enable one to calculate the dispersion coefficient from experimental results. The more general dispersion equation including longitudinal dispersion also was solved numerically to give quantitative limits of a dimensionless group within which the assumption of negligible longitudinal dispersion is justified. Possible experimental procedures were examined, and one utilizing a cylindrical packed column was chosen for the determination of transverse dispersion coefficients. Values of these coefficients were determined for a system of two miscible organic fluids of equal density and viscosity, for two sizes of packing material over a wide range of flow rates in the laminar regime. The dispersion coefficient was found to decrease, for a constant value of the product of packing size and interstitial velocity, as the size of the packing material particles increased. INTRODUCTION Longitudinal dispersion has received extensive treatment in the literature, and consequently is better understood than its orthogonal counterpart, transverse dispersion. Many mathematical models of dispersion processes assume that transverse dispersion is rapid enough to damp out any radial** concentration gradients and therefore may be neglected. Laboratory and production results, however, indicate that this is a poor assumption.l,2 Various experimental procedures for determining transverse dispersion coefficients have been used in previous investigations, but the results have generally been expressed by similar correlations. The transverse dispersion coefficients obtained, however, have often varied considerably for given values of the correlation parameters. We feel that further experimental determinations of transverse dispersion coefficients will help alleviate some of the inconsistencies in these empirical correlations. One assumption implicit in all previous investigations is that of negligible longitudinal dispersion in the experimental system. An attempt to justify this assumption often is made using intuitive reasoning, but it is apparent that this reasoning must break down as the condition of zero flow rate is approached. A mathematical examination of the equations describing the system yields physical limits outside of which the assumption of negligible longitudinal dispersion is invalid. BACKGROUND In a porous medium, the "effective molecular diffusivity" De is less than the molecular diffusivity D measured in the absence of a porous medium, due to the tortuous path which a diffusing molecule must travel. Various authors3-5 have reported values of the ratio De/D in the range of 0.6 to 0.7. When there is fluid flow within the porous medium, mass transfer occurs by convective dispersion as well as by molecular diffusion. These are separate phenomena and can be treated as such on a microscopic scale. However, the mathematical complexity is such that only extremely simple geometries could be considered, and the results hardly would be applicable to the complex geometries existent in actual porous media. A more

Jan 1, 1969

By E. J. Rapperport, J. P. Pemsler

The thermodynamic activities of zinc in six solid solution Cu-Zn alloys ranging from 5 to 35 at. pct Zn were determined experimentally in the temperature range 400° to 600°C. This low temperature investigation was canducted in order to evaluate techniques developed to utilize the inherently high sensitivity of atomic absorption flocesses in the measurement of thermodynamic activities. Analytical expressions ,for the activity and actizlity coeflcient are given for the six alloys in the temperature ranges investigated. RELATIVELY few experimental methods are available for investigation of thermodynamic activities of alloys, especially in the solid state. The techniques most frequently used have been the electrochemical potential and the effusion methods, both of which have severe limitations in many instances. It is therefore desirable to expand the ability to perform such measurements in order to obtain new information as well as to provide an additional independent verification capability. In this work, we present a significant improvement in the spectrophotometric method for sensing small vapor pressures in static absorption cells. Similar techniques have been used previously;1"5 however, applications had been limited to relatively high pressures, often greater than 1 torr. Prior investigators have, for the most part, used broad spectral sources such as xenon or mercury lamps, and high intensity arcs. Hollow cathode sources were first suggested in 1956 6 and were used soon afterwards.4'5 These sources offer significant improvements in sensitivity and freedom from interfering spectral lines.'-' EXPERIMENTAL High purity zinc was obtained from Cominco Products, Inc., and copper from American Smelting and Refining Co. Both elements were of 99.999 pct purity. Copper-zinc alloys were vacuum melted in a high fired carbon crucible with each alloy pulled from the melt as a 4 -in. diam bar. The bars were swaged to -1/4 in. rods and vacuum annealed for 160 hr at 800° + 1°C. Samples for gross chemical analysis were taken at intervals along the length of the rods to ascertain the axial zinc gradient. Electron microprobe analysis of homogenized specimens indicated that the alloys had uniform compositions over their cross sections on a macro (200 p) and micro (1 u) scale to better than *1 pct (20) of the gross composition. This tolerance was determined by counting statistics, rather than assured composition fluctuations. All SiO 2 windows were high-ultraviolet-transmission grade to minimize intensity losses. Silica absorption cells were scrupulously cleaned consecutively in organic solvents, dilute HF, and distilled water before use. The empty cells were then flamed while under a dynamic vacuum, cooled, and removed to an argon-filled glove bag. Alloy pieces were cut and filed in the glove bag to produce fresh surfaces, and then loaded into the cells. The loaded cells were temporarily sealed, removed from the glove bag, reevacuated to 10-5 torr or better, and permanently sealed. The instrument used is schematically shown in Fig. 1. The spectral emission from a commercially made hollow cathode lamp (A) of a selected element is focused through an absorption cell (B) inside a well-controlled furnace (C). The intensity of the transmitted beam is measured using the spectrometer* (D) 'Techtron model AA4 atomic absorption spectrometer. which contains a grating (E) that disperses the light prior to impingement on the photomultiplier (F). The monochromator grating is adjusted so that only the wavelength of interest is measured. The power supply delivered an interrupted voltage to the lamp, causing a chopped radiation output to be transmitted. The detector read only the intermittent component of radiation incident upon it, so that all continuous noise signals (furnace radiation, and so forth) were eliminated. Three recording thermocouples contained in the muffle furnace were positioned along the length of the absorption cell: one at each end and one at the center. An effort was made to keep the ends of the cell several degrees hotter than the center to avoid window condensate. Appropriate thermal corrections were then necessary to relate cell pressure to radiation attenuation. Water-cooled heat shields, as shown in Fig. 1, were found to aid signal stability by protecting the hollow cathode and the photomultiplier from furnace radiation. The furnace had a 2-in. diam muffle, Kan-thal wound, with SiO 2 windows at its ends to minimize convective effects. The hollow cathode radiation was masked and focused to form a conic beam that was a maximum of { in. diam within the furnace. Thus, the 1.5 in. diam absorption cell easily contained the entire beam. The furnace was mounted on ball-bearing slides with positive positioning detents. This arrangement allowed the removal of the entire furnace assembly from the radiation path, position [I], Fig. 1, so that frequent sampling of the unattenuated beam intensity could be obtained. In all cases the beam intensity was kept constant to 0.1 pct as judged by readings taken immediately before and immediately after data collection. Only data for absorptions of less than 80 pct were utilized, as systematic deviations from linearity were found for greater absorptions.

Jan 1, 1970

By A. M. Skov, L. F. Elkins

First response to large-scale water flooding in the fractured very low permeability Spraberry sand has led to a new unique cyclic operation. Capacity water injection is used to restore reservoir pressure. This is followed by marly months production without water irzjection and the cycle repeated. Expansion of the oil, rock and water during pressure decline expels part of the fluids but capillary forces hold much of the injected water in the rock. At least with reservoir pressure restored and with partial water flood development, field performance has proved this cyclic operation is capable of producing oil from the nzatrix rock at least 50 per cent faster and with lower water percentage than is imbibition of water at stable reservoir pressure. INTRODUCTION The Spraberry Field of West Texas presents unusual problems for both primary production and water flooding. Extensive interconnected vertical fractures in the fractional-md sandstone permitted recovery of oil on 160-acre well spacing, but they made capillary end effects dominant. Primary recovery by solution gas drive is less than 10 per cent of oil in place. The concept of displacement of oil from the sand matrix by capillary irnbibition of water has led to field techniques which promise greatly increased oil recovery. Free exchange of laboratory research, reservoir information and results of field pilot tests among the various companies has been very important in development of this technology. Five units covering a total of 170,000 acres have been formed for water flooding, and 10 other areas covering an additional 175,500 acres are in various stages of unitization. Part of the Driver Unit reaching fillup first has demonstrated very unusual waterflood behavior and indicated numerous operating problems that will develop within and among the various units. SPRABERRY ROCK AND PRIMARY PERFORMANCE The Spraberry, discovered in February, 1949, is a 1,000-ft section of sandstones, shales and limestones with two main oil productive members: a 10-15 ft sand near the top and a 10-15 ft sand near the base. In part of the field some thinner intermediate sands are oil productive, and others are water bearing. All sands have permeabilities of 1 md or less and porosities of 8-15 per cent. Ordinary core analysis and electric and radiation logs are ineffective in differentiating between oil productive and nonprcductive sands. Sands capable of containing producible oil are best identified by mercury injection capillary pressure measurement and, in some cases, by core water saturation. About 3,500 wells have been drilled in the 500,000-acre trend. Vertical fractures were observed in practically all Spraberry cores. Continuity and interconnection of fractures were confirmed by pressure interference among wells during early development.' Major fractures trend northeast-southwest as indicated by oriented cores and confirmed by five fluid injection tests, by analysis of the pressure transients observed during development,''' and by three interference tests in the Driver Unit Water Flood reported herein. Fracture spac- ing probably averages inches to a few feet. Spraberry wells typically produced 100-400 BOPD initially after hydrauLic fracture treatments. By 1962 oil production had declined to an average of 12 bbl/well/day, near the economic Limits of operation. Reservoir pressure had declined from 2,300 psi initially in the Upper Spraberry and 2,500 psi in the Lower Spraberry to 500-1,000 psi. Partial closing of the fractures with declining reservoir pressure is believed to be the cause of such low oil production rates at these relatively high reservoir pressures. Cumulative recovery of 208 million bbl of oil is 80 to 90 per cent of that recoverable by primary means. Performance of the entire reservoir is summarized in Fig. 1. IMBIBITION WATER FLOODING By 1952 reservoir performance indicated low primary recoveries. Most engineers, expecting serious channeling of injected fluids through the fractures, held little hope for secondary recovery. With its extensive background of research on the fundamentals of fluid flow within reservoir rocks, Atlantic's Research and Development Division on short notice in 1952 conceived that displacement of oil by capillary imbibition of water into the rock might significantly increase Spraberry recovery. Laboratory data reported by Brownscombe and Dyes scaled to probable reservoir conditions showed potential waterflood recovery equal to or greater than primary recovery with a 10-15 year flood life.= A pilot test using three 40-acre injection wells, one central producing well and 18 surrounding observation wells demonstrated technical feasibility of the process. Injection of 1.5 million bbl of water from November 1952 to August 1955 proved water entered the rock and displaced oil

By E. Douglas Sethness

The uranium industry is booming. In Texas alone, there are about 22 different companies with active exploration programs. Twelve solution mines have been permitted; three surface mines have been authorized; and two mills are currently in operation. However, the industry also has a problem, and that is the disposal of radioactive wastes. Over the past several years, stories concerning nuclear wastes have appeared frequently in the news. One of the most frequently cited cases occurred in Grand Junction, Colorado. In 1966, after ten years of investigations, the U. S. Public Health Service (PHS) discovered that tailings from a uranium mill were being used as fill material and aggregate for local construction purposes. It was estimated that between 150,000 and 200,000 tons of material had been removed and used under streets, driveways, swimming pools, and sewer lines. In addition, tailings had been used under concrete slabs and around foundations of occupiable structures. Further studies prompted the Surgeon General to warn that the risk of leukemia and lung cancer could be doubled at the measured radiation levels. More recently, the L. B. Foster Company discovered that its building site in Washington, West Virginia, was radioactive. While digging a foundation, the ground erupted and a ball of fire 30 feet high shot out. Evidently, the dirt was laced with radioactive thorium and zirconium, a potentially explosive mixture contained in a Nigerian sand which had been used by the previous site owners in the manufacture of nuclear fuel rods. Just this month we have read about legal suits to stop exploration for a nuclear waste disposal site in Randall County, Texas. The U. S. Department of Energy is trying to locate a deep underground nuclear waste depository for final burial of over 76 million gallons of high-level wastes. The problem is acute, the wastes are accumulating at a rate of about 300,000 gallons per year. Nor do these numbers include the spent fuel elements from nuclear power plants that are in temporary storage facilities. Fortunately, public awareness of these and other related issues is high. Unfortunately, the differences in the waste products from the nuclear fuel cycle are not always apparent to the general public. There are two distinct types of radioactive wastes: "high-level", which consist of spent fuel or wastes from the reprocessing of spent fuel; and "low-level", which, in general, are by-product wastes. There are numerous non-technical definitions that can be applied to help the layman differentiate between high-level and low-level wastes. For this latter purpose, it is best to think of them in terms of what we can see and feel. In general, high-level wastes are physically hot and can cause acute radiation sickness in a short period of time. Low-level wastes are not hot, but may cause chronic health effects after long exposure. The wastes which we are concerned with in the uranium mining and milling industry are low-level wastes. As recently as ten years ago, there were very few controls or regulations governing tailings disposal methods. At the same time, mine reclamation was not enforced through either state or Federal laws and the long-term viability of abandoned tailings ponds was not assured. The regulatory climate has changed significantly in the last decade, however. The low-level radioactive wastes generated by uranium mining and milling are generally contained in a tailings pond. Approximately 85-97% of the total radioactivity contained in uranium ore is present in the mill waste that goes to such tailings ponds. The isotope Radium-226 is probably the most potentially harmful radioactive parameter in the ponds. Radium emits gamma radiation and is also an alpha particle emitter. Because gamma radiation is very penetrating, it presents a potential health problem when a source is located external to the body. Gamma radiation will go through the body, causing damage to each cell encountered on the way. Although alpha particles have very little penetration capability, they can cause extensive cell damage. For this reason, alpha particles are a problem after inhalation or ingestion. Radium creates a health hazard by both of these mechanisms. Radium decays to radon gas which can be inhaled and serve as an alpha particle emitter. Additionally, radium is very soluble and readily enters the natural hydrologic cycle if allowed to leach from a tailings pond. With a half-life of 1620 years, radium has plenty of time to be taken into the food chain and end up in our bodies, emitting alpha particles. Because the potential health problems are better understood today than ten years ago, and because the Nuclear Regulatory Commission (NRC) has developed increasingly stringent government regulations, the uranium mining industry applies a high level of technology to the disposal of nuclear wastes. In most cases, low-level radioactive wastes are disposed of at or near the site where they are produced. There are six commercial burial grounds for low-level wastes, but it would not be economical to ship all mine or milling wastes to these sites. The on-site disposal methods most often used are ponding

Jan 1, 1979

By John W. Weeton, Max Quatinetz, Robert J. Schafer

Nickel powders of 1-, 0.4-, and 0.2- average particle size were combined with 0.05- p MgO powder. Oxide was added in quantities of 4, 12, and 20 vol pct. The mixtures were vacuum hot pressed and extruded at 2100°F. In spite of a general tendency to growth of oxide particles during processing, dispersions of fineness comparable to those of Sintered Aluminum Powder, SAP, were achieved. A small amount of oxide considerably improved 1800°F stress-rupture strength, but further oxide addition resulted in a decrease of strength. RECENTLY there has been much speculation concerning the requisites for strong and stable dispersion-strengthened alloys. The nature of the dispersed phase, the stability of the alloys, and variables influencing the mechanical properties of alloys have been given consideration. Such topics have been reviewed by Bunshah and Goetzel. Of the many parameters related to the mechanical properties of dispersion alloys, mean free path between dispersed particles (a measure of the fineness of the dispersion), particle size, and vol pct of the dispersed phase have been shown to be very important. Generally, strength increases with decreasing mean free path, and there is an optimum vol pct of dispersed phase. Just how fine a dispersion ought to be is somewhat open to debate, but Irmann, Lenel, Backensto, and Rose, Gregory and Grant,4 and others have shown in the original SAP-type alloys, aluminum plus aluminum oxide alloys, that better strength is generally obtained with finer dispersions and the best strengths were obtained when the mean free path was less than . Further, Cremens, and rant' showed that in nickel plus aluminum oxide alloys, stress-rupture strength at 1500°F was definitely increasing with decreasing mean free path. In their investigation, however, the finest dispersions that were produced were about 2.0 mean free path. To determine the potential of the nickel plus oxide type of product, it would be neces- sary to obtain dispersions analogous to those of SAP alloys; namely, ones where the mean free path between oxides is less than . Unfortunately, however, it is very difficult to produce extremely fine dispersions of oxides in metals other than those which naturally form refractory oxide skins. There are several approaches to this problem including such procedures as mechanical mixing, internal oxidation, reduction of mixed oxides, and metal deposition from solution. Work at the Lewis Research Center has shown that metal powders 0.1p or finer could be produced by ball milling, when selected grinding aids were utilized.' Because these unusually fine powders were available, it was an initial objective of this study to determine if by mixing of these fine Ni powders with various amounts of MgO (0.05) a fine dispersion of MgO in Ni comparable to those in Al-Al203 might be achieved. A second objective was then to attempt to relate the parameters of structure to 1800°F stress-rupture strength of the alloys. Nickel powders of 1-, 0.4-, and 0.2-p average particle size were combined with 0.05- average particle size MgO powder. This oxide was added in quantities of 4, 12, and 20 vol pct. The mixtures were hot pressed and extruded at 2100°F.

Jan 1, 1962

By E. Martinez

Samples of chrysocolla, a hydrated copper silicate, from several sources were submitted to differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). Pure samples of chrysocolla are difficult to obtain, but comparison of the thermograms revealed that certain reactions occurred in all the samples and it is believed that these are due to chrysocolla. Endothermic reactions occurred at 50' to 175°C, 350° to 650°C, and 980° to 1100°C each of which caused a weight loss. The first was due to loss of absorbed water, the second to a dehydroxyla-tion, and the last to conversion of cupric oxide to cuprous oxide. In addition, two exotherms were detected at 685° to 695°C and 935° to 950°C. Infrared spectra of heated samples indicated the exotherms were due to changes in the Si-O bonds leading to the formation of cristobalite. The results suggest that thermoanalysis may be a more sensitive and reliable method for detection and identification of chrysocolla than X-ray diffraction, infrared spectroscopy, or optical techniques. The recovery of copper from oxide ores has been the subject of much research in recent years. One of the principal oxide copper minerals is chrysocolla, a hydrated copper silicate. The information available indicates that it has widely varying properties depending on the origin of the sample. Chrysocolla usually is found associated with cuprite, malachite, azurite, and native copper. Most of these other minerals are recoverable by present day flotation practice, but chrysocolla is lost in the tailings.1,2 Reagent combinations that are successful in laboratory chrysocolla flotation with ore from one source have been found to be ineffective with another. 3 The copper segregation process offers an altemative to beneficiation of oxide copper ores.4'5 The process is of particular interest in processing ores that cannot be treated by conventional hydrometal-lurgical methods because of high acid consumption.6 Fuller understanding of the properties of chryso- colla may prove of value in the search for improvements in both the flotation and segregation processes. Chrysocolla samples from Arizona, Nevada, Chile, Australia, and South Africa were studied by differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). In addition, a sample from Miami, Ariz., was submitted to X-ray diffraction, infrared spectrophotometry, and surface area determination. EQUlPMENT Differential thermal analysis (DTA) detects, amplifies, and records exothermic-endothermic reactions occurring in a sample as its temperature is raised at a constant rate, usually 10°C per minute. A unit made by the Robert L. Stone Co. was used in this study. The tests can be run if desired with a gas streaming through the sample. A thermobalance records weight losses or gains in a sample as its temperature is raised at a uniform rate. The gravimetric analyses (TGA) were run on a Chevenard thermobalance converted electronically for graphic recording. A heating rate of 5°C per minute up to 1100°C was used in these tests. A Perkin Elmer Infrared Spectrophotometer, Model 221, was used with sodium chloride optics obtaining IR spectra in the 2 to 15 region. A pressed pellet technique with potassium bromide was used in preparing the samples. DESCRIPTION OF SAMPLES Chrysocolla is found in the oxidation zones of copper deposits commonly associated with malachite, azurite, and limonite. It is described as varying in composition and in color from bluish green to brown or black. Inclusions of other minerals are usual so chemical analysis of chrysocolla samples may be suspect. However, it is considered by many to be a solid solution of CuO, SiO2 and H2O with a general formula of CuO.SiO2.2H2O or 2CuO.2SiO2. 3H20. Chukhrov7 has described a sample from the Urals as CU3,5(OH)2 (A1Si3) O10.nH2O and stated that chrysocolla is a montmorillonite-type mineral. On the basis of X-ray analyses, DTA, and infrared spectra of chrysocolla from the Inspiration Mine, Ariz., Sun8 concluded that there was no substantial evidence to classify it as a montmorillonite mineral. Chrysocolla samples from many sources throughout the world were used in this investigation. The following is a brief description of each:

Jan 1, 1963

By Robin O. Williams

AN investigation has been made of the Ni-Cr system for the purpose of elucidating certain points, namely the nature of aging in both terminal solid solutions and the nature of the phase diagram. Information pertaining to solubilities and precipitation has been obtained. Experimentation Five alloys, Table I, were arc melted in a cold copper crucible using electrolytic chromium and car-bony1 nickel, both dry hydrogen treated. These 100 g buttons were homogenized 24 hr at 1300°C in dry hydrogen and air cooled. Powders were prepared by filing or pulverizing and subsequent heat treatment was done in vacuum or helium using titanium chips as a getter. Powder of —80 mesh was filed from the 60 pct Ni alloy quenched from 1000°C and was sealed in silica under vacuum using a 250 °C outgassing. After aging as indicated in Table I1 the lattice parameters were measured on the quenched samples using the standard cos" 6 extrapolation. These parameters are considered accurate to roughly 0.0001A. In all cases chromium lines of 2.8812 ± 0.0005Å at 30°C were found. Drastic quenching from sufficiently high temperatures produced very sharp body-centered-cubic lines in the first four alloys without indications of transformations. Temperatures to 1250°C were used. Solid samples less than 1/16 in. thick were quenched in water without transformation and the powders could be adequately quenched in small helium filled thin wall silica tubing using a water quench. For those powder samples which were quenched from the two phase field the relative intensity of the body-centered-cubic lines and the face-centered-cubic lines were estimated and extrapolated to give the indicated solubility data in Fig. 1. The data for the two higher alloys were somewhat limited, the plotted points being the lowest temperature where no nickel phase was found. Neither filing, abrading, pulverizing, nor cooling to —190°C produced any new diffraction lines for solid samples quenched from the single phase region, nor did the character of the body-centered-cubic lines change Single phase body-centered-cubic powders likewise did not change on cooling to —190°C. Also, samples which had some precipitation due to inadequate quenching showed no additional changes under these conditions. The first change apparent by X-ray diffraction form samples quenched almost fast enough to prevent precipitation was the diffuseness of the body-centered-cubic lines, particularly on the low angle side, For slower cooling rates the diffuse face-centered-cubic lines appeared. Work on the large grained castings showed profuse streaking through some of the Laue spots while oscillating patterns showed broad body-centered-cubic and face-cen-tered-cubic lines as well as some new lines. For the 23.6 pct Ni alloy the new lines corresponded to 2.16, 1.96, and 1.86A and were more similar in character to the face-centered-cubic lines than the body-centered-cubic lines. Samples which were air cooled gave only face-centered-cubic and body-centered-cubic lines which were still broad. One pattern indicated that face-centered-cubic (111) plane was parallel to a body-centered-cubic (110) plane. For those samples which were examined by light microscopy there were details which were not resolved. However, varied and beautiful structures were obtained. Fig. 2 is of an alloy quenched in a helium filled silica tube from the single phase region and shows particles associated apparently with dislocations which are arranged in low angle boundaries. Finer, general precipitation has also taken place within the grains. Figs. 3 to 5 show the variety of structures produced in these alloys on continuous cooling. It appears that there are four distinct modes of precipitation as evidenced by these, figures. Annealing these structures at higher tem-peratures in the two phase field gives structures as shown in Fig. 6, which shows nickel plates in the chromium matrix which reprecipitated nickel on a much finer scale of the final quench. Lower annealing temperatures and shorter times naturally give finer plates of the nickel-rich phase. Samples of the first four alloys were annealed for appreciable times between 900º and 1250°C and gave structures like Fig. 6. The relative amounts of the two phases were measured and extrapolated to give solubility data as indicated in Fig. 1. The point at 1250°C was deduced from data of Oxx.1 These and most of the other samples were checked for ferromagnetism but none was apparent. In fact, it appeared that the magnetic susceptibilities were not more than three times that for paramagnetic chromium. Discussion In Fig. 1 it is seen that the solubility of nickel in chromium can be represented by a slightly curved line on the usual log X vs 1/T plot, These data are believed to be accurate to roughly 5 to 10º. There is only fair agreement with the data of Taylor and

Jan 1, 1958

By Nicholas J. Grant, Ulf Kalling, John Chipman

THE operation of a blast furnace is dependent to an important extent upon the sulphur content of materials charged and the desired limit of sulphur in the product. It has long been known that the blast furnace is the most efficient tool for desulphurization in common use and that this efficiency is associated with the strongly reducing conditions of the hearth and is enhanced by increased basicity and fluidity of the slag. The chemical reactions of desulphurization may be studied from the viewpoint of the ratio of the process or of the final equilibrium conditions. Both kinds of studies contribute to an understanding of the process and both are included here. A simple measure of the desulphurization power of a slag is given by the ratio: Pct sulphur in slag (Pet S) Pct sulphur in metal [Pct S] This ratio was used by Holbrook and Joseph',' to measure relative desulphurizing powers under controlled laboratory conditions. It was also used by Hatch and Chipman3 as a measure of the equilibrium distribution. For the latter purpose it would be preferable to employ thermodynamic activities rather than percentages, but until very recently this has been impossible for lack of data. Now, thanks to the work of Morris and Williams and Morris and Buehl," the effects of carbon and silicon upon the activity of sulphur in the metal are known. The confirmation of this work and its extension to include the effects of other elements by Sherman and Chipman and by Rosenqvist and Cox' make it possible to calculate the activity of sulphur in pig iron of any composition. Hence it is now possible to use data on the equilibrium distribution of sulphur to find its activity in the liquid slag and to approach an ultimate solution of the thermodynamic aspects of the problem. The rate of transfer of sulphur from metal to slag is the problem of major industrial importance and indeed the principal need for equilibrium data has been as a necessary adjunct to the kinetic studies. The rate of approach to equilibrium under laboratory conditions seems slow compared to the requirements of industrial practice, and it is clear that further laboratory studies of rates are needed. In the research reported below, the items which were investigated were the following: I—The role of mechanical stirring on the approach to equilibrium. 2—The role of MgO in desulphurization as compared to CaO. 3—The role of MnO in desulphurization. 4— The limiting reactions which constitute the slow steps in desulphurization. Experimental Procedure The experimental set-up and procedure previously described by Hatch and Chipman" were essentially followed with several small modifications. The graphite crucible containing the slag and metal charge was altered to provide considerably more active stirring and mixing of the slag and metal in the carbon monoxide atmosphere. For this purpose the crucible was machined to provide two deep cylindrical wells which were interconnected at top and bottom as shown in Fig. 1. A graphite screw with a flat thread and of shallow pitch (4 threads per in.) spinning at 600 to 800 rpm was used to lift the slag and metal over the partition between the two wells and throw them over into the second well, where the metal settled through the slag into the reservoir at the bottom. It was possible to see actual particles of slag and metal being thrown over the partition. In this respect, the stirring was more vigorous than used in the work of Hatch and Chipman. A charge of 400 g of wash metal was first melted, and 20 g of FeS was then added to yield a bath containing 1.65 pct S. Immediately 400 g of slag (as pure mixed oxides) was added and fused. The slag was generally fused in 1 hr * 10 min. Within 30 to 45 min after melting, the temperature was adjusted to 1525"C, and the first slag and metal samples were taken. The slag was picked up on the end of a cold Armco iron rod, whereas the metal was sucked into a silica tube. The wash metal composition was (in percent): 4.29 C; 0.022 S; 0.021 P; 0.38 Si. The slags used were of four fixed starting compositions covering a wide range of acid-base ratios shown in Table I. Deliberate variations in MgO were made in these slags to check the role of MgO in blast-furnace desulphurization. Changes due to additions and reactions were followed by analysis of samples. Additions of Mn and MnO were made to most of the heats to note the role of Mn and MnO on desulphurization. Three heats (62 through 64) were made in an open pot induction crucible (graphite) using a

Jan 1, 1952