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By William Glenn

The taking of proper samples of crude ores seems to he less thoroughly understood, or less carefully practiced, than its impor tance requires. We all know how often we encounter the reports of very accurate assays and analyses, the weight of which as evidence wholly depends on the method of obtaining the sample, and is very probably nil, because there has been no proper sampling. Pissages might be cited from technical books, and from current technical literature (all the work of writers whom we delight to honor) to show that even among high scientific authorities there is too little acquaintance with the practical art of the sampler. There is no metallurgical or chemical establishment which does not frequently receive samples truly representing nothing. They consist usually of bits of ore, or what not, selected because they are worse or better than the average of what they are meant to represent. And they are worthless, no matter who made the selection. Where conscious choice is permitted to enter into the operation, a fair sample will not result, unless by a miracle. The work of sampling is often looked upon as within the realm of boys and of pensioners only. At least, though the manual labor be left to subordinates, the principles on which it is conducted and the safeguards with which it is surrounded are not unworthy of the study of experts; and experts should he ready to teach these principles and enforce them in practice. For exact sampling is the indispensable first step towards learning the value of any boxful, carload or shipload of ore. I propose to give a simple account of the method of sampling by hand, such as I have always pursued. There is nothing new about it. So far as I know, it is the immemorial old method, as old at least as Cornish copper-mining. Perhaps my fellow-members in the Institute may suggest improvements in it. If not, it will constitute a record in our Transactions to which laymen and beginners may be referred.

Jan 1, 1892

By G. H. Clevenger

THE reagents now used in flotation consist of various acids or salts, which may be either electrolytes or non-electrolytes, dissolved in water and some substance or combination of substances which function as collecting or frothing agents. At times the only dissolved salts present are those naturally occurring in the water used. The general effect of the electrolyte is to greatly sharpen the separation between the gangue and the concentrate. Examples of this are: The use of sulphuric acid with zinc ores; and of sodium carbonate or calcium oxide (line) with silver-gold ores. Crude pyroligneous acid is also sometimes used when available. Various oxidizing agents, such as permanganates, bichromates, etc., are added in the selective flotation of lead-zinc ores. Many other reagents for performing certain specific functions, either real or imaginary, have been proposed, and a number of them have been tried upon a working scale. The wild orgy of experimentation which is now going on in flotation exceeds even that which followed the introduction of the Washoe process for the treatment of Comstock ores, when, among other things, sage-brush tea and tobacco juice were reagents added to the pans. Out of all this will, of course, eventually come a more or less standard practice for the treatment of each class of ore. Omitting a discussion of the functions of frothing and collecting agents, the reagents used in flotation for this purpose may be classified under five general heads: (1) Essential oils; (2) fixed or fatty oils;. (3) alcohols and their combinations with organic acids; (4) coal tar and its refined products; (5) petroleum and its refined products. A flotative agent of some kind is required in flotation as now practiced. A single reagent, as, for example, certain. of the essential oils, may perform the dual function of frothing and collecting agent, or a mixture of substances may be required.

Jan 9, 1916

By G. E. Agar, P. L. De Bruyn

Flotation is an important example of a chemical process by which one solid may be separated from other solids in a mixture. In contrast to other chemical processes such as leaching and smelting, separation of solids by flotation is characterized by the establishment of contact among three phases. In froth flotation these three phases are the solid to be floated, an aqueous electrolyte solution, and a gas, usually air. The gaseous phase may be re- placed by an organic liquid phase or this organic liquid phase may be added deliberately as a fourth phase. To gain an understanding of the flotation sys- tem, it is therefore necessary to study the chemical and physical properties of surfaces and to establish the effect of changes in composition of the bulk phases on the nature of the three interfaces, solid-gas, solid-liquid and liquid- gas. With very few exceptions inorganic solids are completely wetted by the aqueous phase so that the first step in flotation is to replace partially the solid-liquid interface by a solid-gas interface. This displacement process is accomplished by the addition of suitable reagents to the aqueous phase. The resultant surface reaction leaves the solid surface with a hydrophobic film. Although the primary objective of these reagent additions is to alter the solid surface, chemical reactions between the added chemical species and those species derived from the dissolution of the solids are unavoidable. For a quantitative description of such reactions and for the determination of the feasibility of a proposed reaction, we rely on available thermodynamic data. The application of thermodynamic principles to flotation systems has contributed much to our understanding of flotation. The changes in thermodynamic properties such as free energy and chemical potential are accessible to experimental determination, and a knowledge of their magnitude allows us to develop and predict a chemical mechanism oy which a solid becomes floatable. In this chapter it will be assumed that the reader has a working knowledge of the general principles of thermodynamics and solution chemistry. A complete discussion of the physical chemistry of flotation must include a treatment of solubility relations, complex ionic equilibria, reaction potential, and the elements of electrochemistry, especially those dealing with reversible electrical cells. The principles related to all of these features of the flotation system will not be discussed in this chapter. The discussion will be concerned with the thermodynamics and electrochemistry of surfaces and the electrical double layer model of the interface.

Jan 1, 1962

By Harrison Everett Ashley

(Pittsburg Meeting, March, 1910.) Slimes are usually defined as all material passing a certain-sized sieve, which is invariably the finest sieve employed by each metallurgist in his tests; 100-mesh and 200-mesh have been taken as the limits by different writers in recent volumes of the Transactions ; 150-mesh is common practice. The reader of the first two volumes of Richards 1 is impressed by the inflexibility with which all grinding-arrangements are praised or condemned according as they make little or much slime. Until recently, one of the principal aims of the mill-man was to keep down the slimes. He was obliged to have separate apparatus for sand- and slime-treatment. The latter was sometimes puzzling and erratic. Often it was found most .economical to omit treatment of the slimes entirely, or to store them in immense basins or heaps, waiting for possible future improvements in methods of treatment. Recently, improved processes of agitation and filtration have made possible the successful extraction of values from many slimes. The tendency, when the metal is exceedingly finely disseminated, is to cut out all sand-treatment and to slime everything. These processes have been almost entirely mechanical in their conception, and it is the object of the present paper to show that certain chemical considerations may greatly hinder or assist their successful operation. It has long been a source of dissatisfaction to chemists that their analyses fail to be of much help to the clay-worker; that it is a matter of common occurrence for clays of closely identical ultimate chemical constitution to show the widest possible divergence in physical properties. * Published by permission of the Director of the U. S. Geological Survey. Ore Dressing (1903).

Aug 1, 1910

By H. Kenworthy, R. B. Fisher, R. G. Knicherbocker, M. M. Fine

The progress made to date in the mineral dressing of complex Arkansas titanium ores is reported in this paper. Concentrates of rutile, a dioxide of titanium, were produced by treating a submarginal ore from the Magnet Cove Rutile Co., Inc., Magnet, Ark. The rutile recovery at present is 45 to 50 pct of the total TiO2, with the possibility of increased recovery with additional research. The work reported herein is part of a general study which will later include results of investigation of other titanium ore bodies in the Magnet, Ark., area. The fragile character of the rutile minerals, the softness of the gangue, the occurrence of pyrite and leucoxene, and the considerable proportion of extremely small size rutile in the presence of montmorillonite- and illite-type clays in the Magnet Cove open-pit mine are the important factors in the mineral dressing of this submarginal rutile ore. History The occurrence of titanium minerals in the Magnet Cove area of Arkansas was recognized as early as 1890, but it was not until about 1912 that any appreciable prospecting for the minerals was undertaken. At that time drilling was begun, a shaft was sunk, and several drifts were driven, but beneficiation to recover the titanium minerals was not attempted. The only successful mining and milling operation of the Magnet Cove rutile deposit was begun in 1932 by the Titanium Corp. of America and continued until 1942. The ore was washed by means of a rotary scrubber and then deslimed in a drag classifier. The discharge was ground in a rod mill, classified, and tabled to recover a rougher rutile concentrate, which was screen-sized and retabled on cleaner tables. The cleaner concentrates were given a reducing roast, screen-sized, and magnetically separated to produce a finished rutile concentrate. Most of the rutile produced during this period was sold abroad. In 1942, the Titanium Alloy Corp. of Arkansas (a subsidiary of the Titanium Alloy Manufacturing Co. of New York) purchased the property and rebuilt the mill. Subsequently, the plant and property were acquired by the Magnet Cove Rutile Co., Inc., of Little Rock, Ark., the present owners. Very little titanium has been produced since 1942. Although the Titanium Corp. activities yielded enough returns to allow continued operation for approximately 10 years, certain factors must be recognized. These are: (1) production of rutile in that period was during a low in the economic cycle which permitted low-cost operation on a small scale, and (2) a considerable portion of the production was above the water level and no drainage problems existed. Prior to this paper there has been no published report of any mineral-dressing investigation of the lower levels of the ore body. Reference is made in another paper1 to an earlier investigation of Magnet Cove rutile by the Rolla laboratory, in which it is stated that recoveries of 12 to 17 pct of the rutile were obtained. The present investigation was undertaken to improve the known milling processes and to provide adequate metallurgical information about the ore treatment. Titanium Technology The titanium mineral of primary interest in the present investigation was the titanium dioxide, rutile. Rutile is one of the industrial minerals whose annual consumption is relatively small but strategically important. The domestic production of rutile was 7100 tons in 1948. The imports of rutile in the same year were approximately 8000 tons.2 A major use of rutile is in the production of welding-rod coatings, for which a product containing a minimum of 92 pct titanic oxide is desired. Other constituents, such as lime, silica, and sulphur, must be held to a minimum, but hard-and-fast specifications for these elements cannot be drawn. It is necessary to incorporate the rutile in a welding-rod coating, make a sufficient number of test welds, and then determine the tensile strength of the weld metal in the as-welded and stress-relieved conditions. Such a test gives

Jan 1, 1950

By George C. Fryburg

The oxidation of platinum at high temperatures (above 800°C) is controlled by boundary-layer diffusion, except at the lowest pressures. The rate of oxidation is determined by the rate of diffusion of oxide through the boundary layer away from the platinum. This is in contrast to the situation in tungsten and molybdenum oxidation, where the rate is controlled largely by the diffusion of oxygen through the boundary layer towards the metal. The difference in mechanism is a consequence of the much lower rate of oxidation of platinum. Evidence is presented that supports this mechanism for the oxidation of platinum. SOME years ago we reported1 a study of the oxidation of platinum in ordinary oxygen in the temperature region above 800°C, where the oxide is volatile. All the data available up to that time had been obtained with platinum crucibles or plates heated in tube furnaces. The results were widely variant and highly dependent on the flow rate of gas through the furnace: the faster the gas flow rate, the higher the measured oxidation rate. These results indicated to us2 that reaction equilibrium was being approached in the furnace and that the rate was diffusion limited. To minimize these effects, we employed1 electrically heated ribbons placed in a cooled bulb. We were primarily interested in the low-pressure region, but some experiments were performed at pressures up to 1 atm. We found a peculiar pressure dependency which was explained on the basis that the rate of oxidation was proportional to the pressure at all pressures, but that with increasing pressure an increasing fraction of the volatilizing oxide was back-reflected to the ribbon by the surrounding gas molecules. The oxide molecules are not stable at the temperature of the platinum and are decomposed on impact, the platinum being re-deposited on the specimen. Because of the limitations of space, this explanation was offered summarily without detailed support. Recently, Jaffee and associates3, 4 have suggested that the pressure dependency of our data up to 0.5 torr could be explained on the basis of a Langmuir-type adsorption of molecular oxygen followed by dissociation. Since the correct explanation of the effect of pressure on the oxidation rate is a necessary requirement to the development of the basic mechanism of the oxidation reaction, we felt that the back-reflection theory should be presented in more detail. This is the object of the present paper. RESULTS AND DISCUSSION A typical set of results showing the pressure dependency of the oxidation reaction is presented in Fig. 1, where we have plotted, on logarithmic scales, the rate of oxidation, R, vs the pressure, p. For comparison some results of Krier and Jaffee4 and of Raub and plate5 are also shown. These data were taken at atmospheric pressure using furnaces. The effect of reaction equilibrium within the furnace is apparent from the much smaller values that these observers obtained: Raub and Plate In O2 found a rate of 3.1 µg cm-2 hr-1 compared to our value of

Jan 1, 1965

By Joe O. Ledbetter

INTRODUCTION Health physics as a profession really got a significant start during the Manhattan Project of World War 11. The Health Physics Society has recently published its 25th anniversary issue of the journal (June 1980). There was concern over radiation exposures during and after uranium production, especially about radium and its daughter products [Jackson 19401 and, as evidenced by the frequency of articles in the literature, there still is. The reason for this concern was expressed by Harley as "Workers engaged in the mining and pro- cessing of radium-bearing materials are exposed to dusts of the parent, to radon, and to the radon daughter products. In- haled radioactive particulates may be retained in the lung or redistributed to other organs of the body. Relatively minute de- posits of radioactive substances, particularly alpha emitters, have been clearly shown to be the etiological factor in a variety of injuries to industrial and re- search workers. " [Harley 1953] Emphasis in measurements has been placed on radium in water and radon in air, since these are the principal mobilized phases; however, it should be kept in mind that radium-containing particles do become suspended in air as aerosols and radon absorbs in liquids. Much of the uranium mining and production is being carried out aboveground. The principal difference between underground and surface (pit or leach) mining of uranium is the reversal in the relative importance of roles for the types of radiation dose. For aboveground the major radiation exposure is external gamma ray, whereas for underground it is internal alpha; for aboveground, the whole body penetrating is of greater importance than the lung alpha dose. AS a result of the politics involved and the law- suits for any and all diseases as being occupationally- caused, today , more than ever before, the successful performance of the activities connected with uranium production--before-, during-, and after-the-fact-- must include the provision of first class radiation protection. Such protection can be achieved by good measurements, thorough risk evaluations, and adequate controls. Meeting the ALARA (As Low As Reasonably Achievable) philosophy necessarily entails the determination of what is reasonable exposure. The necessary and sufficient elements of radiation safety under the ALARA dictum require a hard look at the dose versus effects data. There are times when the health physicist needs to make decisions of judgement rather than compliance with a well-defined regulation value. In order to facilitate such decisions, the real world must be separated from opinions that are merely artifacts of statistical variation and from the unprovable "what ifs" that are slanted to question the morality of any non-Luddite. UNITS VOCABULARY FOR DOSIMETRY There have been many radiation quantifying and dosimetric units introduced in the past. Fortunately, most of them did not catch on enough to become required knowledge for reading the health physics literature. The unit definitions necessary for our purposes here are the following: -curie (Ci)--unit of radioactivity equal to 3.7 x 10 10 disintegrations per second Webster&apos;s 19711 or the quantity of radionuclide that undergoes 3.7 x 10 nuclear transformations per second. Environmental levels of radioactivity are usually measured in picocuries (10-l2 Ci) per cubic meter for air and in picocuries per liter (pCi/~) for water and sometimes for air. .roentgen (R)--exposure dose of x or gamma rays that gives 1 esu of charge (either sign) to 1 cc of dry air @ STP. The roentgen is equivalent to an energy absorption of 86.7 ergs/g of air [Gloyna and Ledbetter 19691. .rad--radiation absorbed dose of 100 ergs per gram of absorber. The SI unit for absorbed radiation dose is the Gray; 1 Gy = 100 rads. orem--radiation absorbed dose of 1 rad times the quality factor (QF) for that radiation. The QF is 1 for x rays, gamma rays, beta rays, and posi- trons. For heavy ionizing particulate radiation, QF is a function of the amount of energy trans- ferred per unit length of travel, i.e. , the linear energy transfer (LET); the values of QF:LET in keV/um are as follows: 1:<3.5; 1-2:3.5-7; 2-5:7-23; 5-10:23-53; and 10-20:53-175 [Morgan and Turner 19 671 . For radiobiology, relative biological effectiveness (RBE) is recommended for use instead of the quality factor above that is for radiation protection: the RBE is the ratio of the dose of 200 kVp x rays to the dose of radia- tion in question (both in rads) to cause the same

Jan 1, 1980

By J. T. Norton, N. J. Grant, A. M. Gervais

An investigation of the creep deformation of coarse-grained high-purity aluminum at temperatures approaching the melting point permitted the formulation of a theory of subgrain formation. Subgrain boundaries were found to be formed by two different processes: kinking and polygonization. Polygonization is considered as the main factor in subgrain formation. SINCE "slipless flow" was first discussed in detail by Hanson and Wheeler,&apos; many studies have been undertaken to determine how metals deform at high temperatures. Several types of observations have been reported. Jenkins and Mellor,² working on the creep of mild steels and various grades of commercial irons, found metallographic evidence of a kind of substructure within the grains after deformation at high temperatures. Homes" observed after creep deformation of steel at high temperatures that the original X-ray spots were sharply divided into several small ones. The same phenomenon was reported by Hirst4 from his studies on lead and later by Crussard5 from his work on aluminum. The works of these investigators demonstrated beyond any doubt that the splitting of the X-ray spots was due to the fact that the grains underwent a division into subgrains during deformation at high temperatures. Since then, numerous experiments have been undertaken on aluminum in order to determine the mechanism of formation of subgrains. Research workers can be divided, for the purpose of discussion, into two different groups as regards thinking on subgrain formation. On one hand, based on the work on polygonization by Cahn,6 Guinier and Lacombe,7 Greenough and Smith," Crussard,10,11 and Servi, Norton, and Grant," it was concluded that subgrain formation was a consequence of the simultaneous effects, first, of inhomogeneous deformation which produced bending of the lattice, and second, polygonization. On the other hand, Wood and coworkers13-16 based their work on the results of an earlier report" which dealt with crystallite size and a fragmentation theory. It is interesting to note that while Greenough and Smith8 and Wood et al. performed similar experiments, their conclusions were quite different. Wood et al. did not recognize polygonization as a fundamental mechanism and said that aluminum, at the beginning of the deformation, fragmented immedi- ately into subgrains in order to permit deformation of the metal, the number of these subgrains being a function of strain rate and temperature. They concluded that deformation of grains occurred by flow along the subgrain boundaries. In view of the contradictory conclusions, it would appear that the data were not explicit enough to provide an unambiguous conclusion. It appears that the techniques by which most of the results were obtained, namely, X-ray work, were not enough by themselves to solve the problem. Another approach was needed. In the present research, therefore, an extensive metallographic study was planned to supplement the X-ray work. The importance of revealing the subgrain boundaries metallographically was realized, and this will explain the extensive development and use of etching techniques. In order that subgrains would be considerably larger and therefore more readily visible under a microscope, the creep experiments were performed at very high temperatures approaching the melting point of aluminum. Development of Experimental Technique Creep tests were run at constant load on high purity (99.995 pct) aluminum specimens having a very coarse grain size. None of the specimens was run to fracture. The specimens were originally round (diameter, 0.187 in.; gage length, 1 in.) and had parallel flats milled in the gage section to permit

Jan 1, 1954

By Jeremias K. Chitunda

Significant cost savings and improved ground stability are two initial indications from the current wet process shotcrete ground support program at the Lakeshore mine. The area of shotcrete for ground stability is not strange to the Lakeshore operation. Since the beginning of the project, various shotcrete techniques have constantly been experimented with, incorporating all the latest technological developments. Over the years, the use of shotcrete has been employed as a primary, temporary, or permanent support, singly or in combination with rockbolts and steel sets. The extent of shotcrete usage compared with steel sets and rockbolts has varied from time to time as dictated by the overall state of the art. In 1972, for example, the ratio of the linear drift footage supported with shotcrete to that supported with steel sets averaged 1.0. In 1973, that ratio was about 3.0. Overall, for the Lakeshore mine, there are about 8000 drift ft of shotcrete, 8000 drift ft of steel sets and timber, 750 drift ft of formed concrete, 21,000 drift ft of rockbolts, and 3700 drift ft of combined type support.

Jan 12, 1974

By E. C. W. Perryman

The recovery and recrystallization characteristics of superpurity aluminum have been investigated using electrical resistivity, X-ray line breadth, and hardness measurements for the former and the micrographic method for the latter. The three different properties recover at different rates and have different activation energies. The recrystallization results agree well with Avrami&apos;s theory and furthermore indicate that the perfect subgrains formed during recovery are not the nuclei for re-crystallization. WHEN a metal is plastically deformed, its physical and mechanical properties generally undergo considerable changes and by subsequent annealing these changes are partly or wholly annihilated. Thus, a recovery process can be discussed, taking this term in its general sense. In practice, however, there is reason to discriminate between two apparently different processes, one most easily followed at low temperatures, in which the properties return to an almost constant value between that of the cold worked and fully annealed material, and a second process in which the properties return to their original values before cold working and which is accompanied by the formation and growth of new grains having an orientation different from that of the matrix. In this paper the word recovery will be taken to mean the changes in some property as a function of annealing time which occur either without the appearance of new grains or under conditions such that the new re-crystallized grains are very small (= 2 microns), are very few in number, and substantially do not affect the property being measured. This definition is rather abitrary, for it will depend upon the sensitivity of the technique used for the observation of new recrystallized grains, which in the present work was about 1 to 2 microns. However, it is helpful to use the term recovery in this sense and to reserve the term recrystallization for the processes of nucle-ation and growth of new grains in the cold worked matrix. Although considerable work has been done on recovery and recrystallization, most workers have based their study on the measurement of one or perhaps two parameters. Since very small amounts of impurities have such a profound effect on the recrystallization characteristics of a pure metal, it becomes extremely difficult to correlate one piece of work with another. With this in mind, the present work on recovery and recrystallization was done on the same material. Experimental Procedure Material Used and Fabrication: The composition of the superpurity aluminum used throughout this investigation was 0.002 pct Cu, 0.003 pct Fe, 0.003 pct Si, and <0.001 pct Mg. The ingot was hot rolled to 0.250 in., annealed, and cold rolled to 0.034 in. A large number of reductions and intermediate anneals were carried out so as to produce material with a minimum of preferred orientation and maximum homogeneity. For the recovery part of the investigation, the final cold reduction was 20 and 80 pct and for the recrystallization part, 20 pct. After each pass in the cold rolling process, the material was quenched in cold water in order to keep the rolling temperature as near room temperature as possible. Annealing Procedure: For the recrystallization work, specimens 1x1 in. were cut from the 0.034 in. cold rolled sheet and a hole was drilled in each through which a wire was threaded to support it in the salt bath. The temperature of the salt bath was controlled to +2°C and the time taken for a specimen to reach temperature was approximately 5 sec. These 1 in. squares were then divided into three groups, one of which was given 5 min at 318°C and another 2 hr at 244°C. These treatments were such that recovery was almost complete and a well defined subgrain structure produced. Separate specimens of each group were annealed for different times at 301°, 318°, 355°, and 373°C, i.e., three specimens for each annealing time. The delay between finish of cold working and start of annealing was about 1 hr. For the recovery work, strips 0.062 in. thick were cut from the cold worked sheet, annealed, and then given the last cold rolling operation. This was done for each annealing temperature. By this means it was possible to minimize the delay between cold working and annealing. In general, all measurements were carried out within 1 hr of the last cold rolling operation. Annealing at low temperatures was done in an oil bath the temperature of which was maintained constant to +1°C. Electrical Resistivity Measurements: Strips 20x0.5x0.05 in. were machined and the electrical resistance measured using a Kelvin double bridge. Measurements were made in an oil bath maintained at 20rt0.1°C. The same specimen was used for the complete isothermal annealing curve.

Jan 1, 1956

By G. R. Love, M. L. Picklesimer

Aboue 950°C the Nb-Zr system consists of a completely miscible bcc solid solution, commonly called the phase. Between 950 and 600°C, and between 20 and 85 pct Nb, the phase deconlposes, after sunciently long times, into two bcc solid solutions. The pct Zr alloys are conveniently descibecl with T-T-T (time-temperature-transformation) curves having a nose at about 2 hr at 700°C. The reaction rate varies only slowly with zirconium content and negligibly with oxygen contanzination; it is speeded up by a factor of 10 to 15 by 90 pct cold ulork and slowed dou by n factor oj 10 to 30 by a two-hundrecljold increase in grain size. Nb-r alloys with compositions between 40 and 85 pct Nb have been the basis for the majority of commercially important superconducting materials. In part because of their commercial promise, more is known about these alloys than about most other high-field superconducting materials. At the same time, there is considerable disputed or incomplete metallurgical information. For example, although Rogers and tkins&apos; indicate a monotectoid reaction at approximately 600°C and a two-phase 01 + 0, field extending between 20 and 85 pct Nb and to a maximum of 95OGC, erhout&apos; has reported that this entire region would be a single homogeneous B were it not for oxygen contamination. Again, although it has been shown that relatively short-time heat treatments in the vicinity of 700CZ significantly improve the ability of short wire samples to carry high currents in high magnetic fields at 4.2K, these observations have never been fully correlated with the structural change or changes occurring during the anneal. We intend to investigate in detail the effect of metallurgical variables, including heat treatment, on the superconducting properties of hard superconductors. To verify that our experimental techniques are valid and to establish a relative standard against which other materials may be measured, we feel it advisable to know the behavior of the Nb-Zr alloys under a variety of processing conditions. As an initial step toward this goal, we have determined in detail the kinetics of the transformations in Nb-Zr alloys. EXPERIMENT A number of problems had to be solved before beginning any fruitful work on the reaction kinetics in this system. While solving some of these problems, either by chance or by design, small amounts of information were obtained about alloys containing 40, 50, 60, 65, 67, 70, and 75 pct Nb, bal. Zr. In addition, a large range of grain sizes and a range of temperatures considerably greater than the range indicated by Rogers and Atkins phase diagram were examined. We will, however, report in detail only the results obtained for the Nb + 33 pct Zr and Nb + 25 pct Zr alloys at three grain sizes, two levels of oxygen contamination, and the temperature range 550 to 950°C. These data are most complete, but the other data are sufficiently complete to indicate the kind and magnitude of the variation of the transformation kinetics outside this range. The first and most difficult problem encountered in this inquiry was one of sample homogeneity. When Nb-Zr alloys are arc- or electron-beam-melted on a cooled copper hearth, solidification is sufficiently slow that there is appreciable coring in the cast structure and a large variation of grain size across the button thickness. Both these factors significantly affect the apparent reaction rate in the system. A two-step solution to the problem was attempted; an arc-melting and drop-casting technique has been developed by conald that greatly reduces the as-cast grain size and virtually eliminates coring segregation. Ingots made in this way exhibited no detectable (3 pct maximum) zirconium segregation. Before it was evident just how good this technique was, we attempted to supplement it with rather long-time, high-temperature annealing of the cast ingots. This annealing was carried out in evacuated and sealed (seal-off pressures < 1.0 x 106 torr) quartz capsules lined with tantalum foil at 1400 to 1450 C for 8 to 72 hr. There were two principal effects of this treatment: the grain size increased to a fairly uniform 150 p, and the surface and all grain boundaries near the surface acquired a film of a second phase, tentatively identified as an oxide (possibly additionally contaminated with silicon). There was no evidence that this 1400 C treatment had affected the zirconium segregation. High-temperature annealing was subsequently used only for grain-size control, but anneals of longer than 4 hr at temperatures greater than 1000°C were performed in dynamic vacuums (pressure no greater than 1.0 x lo torr). Any contamination resulting from these treatments was well below the limits of detection of our techniques. All samples, as cast, were cold-swaged to at least 85 pct reduction in area. The samples called cold-worked were tested as swaged. The minimum re-crystallization anneal for these alloys was about 12 hr at 1050 C; this produced an equiaxed grain diameter of about 4 to 8 P. Annealing for 4 hr at 1450°C produced a grain size of about 80 to 150 p; and annealing for 4 hr at 1650aC, close to the melting point of many of these alloys, produced a grain size of 0.5 to 1.0 mm. At all temperatures, the larger grain size was

Jan 1, 1967

By J. B. Conway

Stress-vuptuve data for several of- the refractory metals are frequently found to yield a linear relationship between the Larson-Miller parameter and the logarithm of the applied stress. In such cases linear stress-rupture isotherms result with slopes bearing a definite relationship to the temperature. It also follows that the stress to produce rupture in a certain period of time will be linear in temperature. Data for several refractory metals have been reviewed and excellent linearity is shown in this type of isochronal plot. In addition, the af ore - mentioned lineavity leads to a linear relation between the log of the stress to produce rupture in a certain time and the homologous temperature. This has been illustrated for the Group VI-A metals, tungsten and molybdenum. EXTENSIVE use has been made of the Larson-Miller&apos; parameter in the interpolation and extrapolation of stress-rupture and creep data. In those cases where this particular parametric approach is applicable a convenient and fairly straightforward procedure is made available for the correlation of experimental stress-rupture data. It is quite common to employ this parameter in the form of a master rupture plot in which the parameter, T(C + log tr), is expressed as a function of log stress. In many cases this functional relationship in log stress is linear within acceptable accuracy and hence the following relation results: where P is the parameter, C is the Larson-Miller constant, T is the absolute temperature, t~ is the rupture time, a is the stress, and a and b are constants. Examples of such a relationship are contained in the work of Green, Smith, and 01son2 dealing with high-temperature rupture behavior of molybdenum and in the work of Green&apos; dealing with the high-temperature behavior of tungsten. In addition, pugh4 has shown a similar linearity for some fairly low-temperature data for molybdenum. It can be shown that when the relationship in Eq. [I] is exhibited certain generalizations can be made concerning the form of the stress-rupture isotherms. For example, rearranging yields: For a given material (constant C) at a given temperature the first term on the right-hand side of Eq. [2] is a constant and hence this equation defines a straight line when log stress is plotted as a function of log-rupture time. This is recognized as the standard form usually employed in this type of data presentation. Such linearity then suggests the linear form of the Larson-Miller parameter. Or, in other words, the linear parametric relationship in Eq. [2] results only when the stress-rupture data are linear on a log-log plot of stress vs rupture time. Another interesting observation can be made in regard to Eq. [2]. It can be noted that the slope of the stress-rupture isotherms is given by - T/b and hence a direct calculation of the constant b is available. It also follows that since the value of b is the same for all temperatures the slopes of the various isotherms on the log-log stress-rupture plot cannot be the same. Indeed, the existence of the relationship in Eq. [2] precludes a system of parallel lines on this common stress-rupture plot. As a matter of fact it further specifies that in addition to being nonparallel the slope of these isotherms must decrease (i.e., become more negative) with increasing temperature. Such a condition is indeed found to exist in the case of the stress-rupture data reported for molybdenum.&apos; As a corollary to the above, it may be stated that stress-rupture data which do not lead to a linear log-log stress-rupture plot or whose isotherms do not exhibit a decrease in slope as the temperature increases will not yield the linear relationship of Eq. [I]. Applying Eq. [2] to two different temperatures and solving for C yields: Eq. [3] affords a simple and rapid method for calculating the Larson-Miller constant from the log-log stress-rupture plot. The slope of a given linear isotherm is measured and the value of "b" calculated based on Eq. [2] as: slope = - -Tb Then at an abscissa value of 1.0 hr (making log tr in Eq. [3] equal to zero) read the stress corresponding to rupture for two different temperatures. Substitution in [3] yields: A value of the Larson-Miller constant can thus be calculated from a few simple mathematical procedures employing data read directly from the log-log plot of the stress-rupture data. Of course, it is not to be overlooked that the above reasoning has been based on the linear relationship of Eq. [I] being applicable. However, if as mentioned above the log-log plot is

Jan 1, 1967

By L. W. Holm

Laboratory flooding experiments on linear flow systerns indicated that high oil displacement, approaching that obtained from completely miscible solvents, can be attained by injecting a small slug of carbon dioxide into a reservoir and driving it with plain or carbonated water. Data are presented in this paper which show the results of laboratory work designed to evaluate this oil recovery process, particularly at reservoir temperatures above 100°F and in the pressure range of 600 to 2,600 psi. Under these conditions CO2 exists as a dense single-phase fluid. It was found that a bank, rich in light hydrocarbons, was formed at the leading edge of the CO? slug during floods on long cores. Formation of this bank is probably due to a selective extraction by the C02 and, it is believed, partially accounts for the attractively high oil recoveries. In crddition to the efficient displacernerlt of oil from the pores of the rock by this process, the favorable rnobility ratio related to a C0 2-water flood also contributes to high oil recovery. A further advantage of this process is noted on limestone and dolomite rock, in that the CO1 reacts with the porous medium increasing its permeability. Flooding experiments were conducted on sandstone and vugular dolomite models. The results of this experimental work show the effect on oil recovery of type of porous medium, pore geometry, flooding length, and flooding pressure. The porosity of the cores and rilodels varied from 16 to 21 per cent and their pern~eabilities ranged from 100 to 200 md. A reconstituted West Texas reservoir oil, a West Texas stock tank oil, an East Texas stock tank oil and Soltrol were used to represent reservoir oils in this study. Oil recoveries ranging from 60 to 80 per cent of the original oil in place in these cores were obtained by CO2,-carbonated water floods at pressures between 900 and 1,800 psi, compared with conventional solution gas drive and water-flood recoveries of 30 to 45 per cent on the same cores. Oil recoveries greater than 80 per cent resulted frorn f1oods at pressures above about 1.800 psi. There high recoveries were noted from both the sandstone and the irregular Porosity carbonate cores. In all floods, additional oil was recovered by a solutiorr gas drive resulting from blowdown following the flood. Oil recoveries of 6 to 15 per cent of the original oil in place were obtained during this blowdown period. This additional recovery was found to be a function of oil remaining after the flood, decreasing with decreasing oil saturation. It was also noted that highest oil recoveries by blowdown were obtained when carborlated water rather than plain water followed the CO, slug. INTRODUCTION Miscible phase or solvent flooding processes, which are designed to increase oil recovery -from petroleum reservoirs, involve the injection of small quantities of a petroleum solvent into the reservoir, followed by an inexpensive scavenging fluid which is miscible with the solvent. Essentially complete displacement of oil from the pores of reservoir rock has been obtained by this technique. CO,, although not completely miscible with most reservoir oils at moderate pressures, is highly soluble in these oils at pressures above about 700 psi; there is appreciable swelling and reduction in the viscosity of oil when CO, is dissolved in it. Therefore, CO, could be expected to perform similarly to other oil solvents as a displacing agent. CO, is also highly soluble in water at elevated pressures, so water should be a satisfactory material to drive a slug of CO, through an oil-bearing reservoir. A favorable mobility ratio would be obtained through the reduction in viscosity of the oil and the use of water as a final displacing agent. A number of investigations of the use of CO, to improve oil recovery have been reported in the literature.2,3,4,5,6 These studies, however, have been conducted on uniform porosity sandstone at relatively low temperatures and pressures. The behavior of CO1 as a flooding agent at temperatures above its critical temperature could not be predicted adequately from these studies, particularly for the case of non-homogeneous rock. The purpose of this work was to evaluate the oil recovery efficiency of a process involving the injection of a CO2 slug followed by carbonated water, at reservoir temperatures above 100°F and in the pressure range of 600 to 2,600 psi, and to compare this process with conventional water flooding. The investigations were primarily designed to provide information on the efficiency of the process in irregular porosity carbonate rock. The effects of flooding path length, the presence of free gas, the type of oil to be recovered, and the amount of solvent required were also determined. The essential results of static phase behavior studies and experimen-

By George S. Barnett

The Equis and El Roble projects are located in the Cordillera Occidental of Colombia. The Equis vein deposits have sulfide ore reserves of 95,955 mt (105,770 st) grading 8.51 g/mt (0.248 oz/st) gold and 12.4 g/mt (0.36 oz/st) silver with 0.94 % copper, 1.10 % lead and 11.06 % zinc. Ore reserves at El Roble are estimated as 1.1 Mmt (1.21 million st) grading 4.89 % copper and 3.39 g/mt (0.099 oz/st) gold. Geologically possible reserves at Equis may total 1.6 Mmt (1.76 million st). El Roble has the potential to contain several tens of millions of metric tons. Exploration included diamond drilling, trenching, channel sampling, rock and soil geochemistry, geophysics and tunneling. Erratic high grade samples affect the weighting of channel and drill core samples. Secondary reconcentration of gold is also a factor. Sample maps and graphs show the distribution of values to be highly variable. Geostatistical treatment of some of these data gave important guidelines for parameters such as sampling densities, drill hole spacing and confidence limits.

Jan 1, 1985

By Hans Lundberg

By electrical prospecting, orebodies that do not otherwise manifest themselves at the surface may be located. Conditions favorable to success with the methods are: Favorable geological conditions, such a proportion of minerals of good electrical conductivity in the orebody as will render the latter materially a better conductor than the enclosing rock, situation of the orebody within the range of influence of the electrical currents used and in proportion to this range a sufficient area of horizontal cross section of the orebody. The result is to permit of spotting drill holes accurately and to save the expense of drilling barren ground. THE art of prospecting, like other branches of mining, has developed rapidly during the last ten years, mainly because of the advancement of mining geology, but also because of the development of "geophysical methods," which are based on the different physical characters of minerals and rocks, e. g., specific gravity, elasticity, and magnetic and electric properties. These methods have proved of great value, especially in countries where the rock is covered by soil and direct geologic investigation is out of the question. In prospecting for orebodies, the methods based on studying differences in electrical conductivity have proved most successful; for which reason, the methods of electrical prospecting have been subject to the most energetic and systematic work, especially in Sweden. This paper gives a brief description of the methods of electrical prospecting now in use, especially the new electromagnetic methods, which have not been described before. The great differences in the electrical properties, especially in conductivity, between ore minerals and rock minerals are fundamental to all methods of electrical prospecting, for which reason, the electrical conductivity of ore minerals and rock minerals has been carefully studied in connection with and previous to the development of the various methods of prospecting with electricity. Ore minerals with a metallic luster, such as chalcopyrite, iron pyrite, galena, specular iron, magnetite, etc., also graphite and a number of cows, have considerably higher conductivity than the surrounding rock and soil (see Table 1). The figures of the table denote the specific resistance W, expressed in ohms for a cube with an edge of 1 centimeter.

Jan 7, 1925

By Howard S. Bryant

Kansas maintained its fourth position on the list of all oil-producing states, for the ninth consecutive year. Total crude-oil production during 1935, as reported by the Oil & Gas Journal, was 53,364,446 bbl. on 97 per rent tank table calculations. This represented an increase of 17 per cent over the production in 1934, which had been the all-time peak of production in Kansas up to that time. Many of the 51 new discoveries of the year, listed in Table 2, did not have a pipe line outlet until about January, 1936; therefore did not contribute to the 1935 production of the state. The potential of all wells in Kansas at the end of the year was 998,-000 bbl. per day, and the daily allowable was 143,000 bbl. per day, showing proration to the extent of 14 per cent of capacity, under the rules of the State Corporation Commission. Several important new pipe lines were built into western Kansas by extending older lines from east to northwest, providing additional outlets for new crude-oil production, and increasing the service facilities from the older oil fields. The crude-oil price level remained unchanged throughout 1935 as it did in 1934, the price of Kansas 36" gravity crude being quoted at $1 per barrel. However, on Jan. 9, 1936, the price of this gravity oil was raised to $1.10 per barrel. Following the trend of the past several years, drilling activity was largely in western Kansas, and showed a still farther westward push from last year. A relatively high percentage of successful wildcat wells at a relatively shallow drilling depth, combined with the expiration of leased acreage assembled before the depression, caused the rapid exploration and development campaign, begun in 1934, to continue. This has caused the opening of more new fields in 1935 than during any previous year in the history of oil production in Kansas. A summary of the results of drilling in western Kansas is given in Table 2. Eastern Kansas had considerable drilling, showed six new fields or extensions of oil fields, but in the limited space of this paper such developments cannot be described.

Jan 1, 1936

By Howard S. Bryant

Kansas maintained its fourth position on the list of all oil-producing states, for the ninth consecutive year. Total crude-oil production during 1935, as reported by the Oil & Gas Journal, was 53,364,446 bbl. on 97 per rent tank table calculations. This represented an increase of 17 per cent over the production in 1934, which had been the all-time peak of production in Kansas up to that time. Many of the 51 new discoveries of the year, listed in Table 2, did not have a pipe line outlet until about January, 1936; therefore did not contribute to the 1935 production of the state. The potential of all wells in Kansas at the end of the year was 998,-000 bbl. per day, and the daily allowable was 143,000 bbl. per day, showing proration to the extent of 14 per cent of capacity, under the rules of the State Corporation Commission. Several important new pipe lines were built into western Kansas by extending older lines from east to northwest, providing additional outlets for new crude-oil production, and increasing the service facilities from the older oil fields. The crude-oil price level remained unchanged throughout 1935 as it did in 1934, the price of Kansas 36" gravity crude being quoted at $1 per barrel. However, on Jan. 9, 1936, the price of this gravity oil was raised to $1.10 per barrel. Following the trend of the past several years, drilling activity was largely in western Kansas, and showed a still farther westward push from last year. A relatively high percentage of successful wildcat wells at a relatively shallow drilling depth, combined with the expiration of leased acreage assembled before the depression, caused the rapid exploration and development campaign, begun in 1934, to continue. This has caused the opening of more new fields in 1935 than during any previous year in the history of oil production in Kansas. A summary of the results of drilling in western Kansas is given in Table 2. Eastern Kansas had considerable drilling, showed six new fields or extensions of oil fields, but in the limited space of this paper such developments cannot be described.

Jan 1, 1936

By Paul Tyler

THE ferroalloying elements are connecting links between the steel industry and the nonferrous metal industries. Although ferroalloys are distinctly nonferrous themselves, they serve the steel industry either in the manufacturing process or in modifying the product-in some cases so that it may compete in the markets with nonferrous metals. Of the 92 elements generally accepted by chemists as constituting the primary building blocks of matter, all but the very rarest have been investigated with a view to employing them in steel manufacture. The surprising thing is that so few have been found commercially acceptable. Despite the relatively small number of elements involved, the employ-ment of alloys in steelmaking is one of the most complicated and probably one of the least well understood of modern industrial enterprises. A great deal has been written regarding the action of individual elements and a profuse and somewhat acrimonious literature covers pretty much the whole field of ferroalloy ore supplies. In the middle ground between the miner and the steelmaker developments are less carefully watched by most observers, and except for an occasional description of the technique of some conversion process or the tariff hearings in Congress, very little is said about them. The purpose of the present paper is to describe in relatively nontechnical terms this highly complex industry and to study its relations to our national progress.

Jan 1, 1933

By D. T. Peters

To better understand the Co-Mo interaction in maraging steels, the precipitate reversion behavior of two alloys closely related to the 18 Ni-250 grade has been studied. The reversion experiment is carried out by aging at a low temperature, T1 (preaging temperature), for some period of time and then aging at a higher temperature, T2, called the reversion tetnperature. Aging and reversion tmzperatures used were in the range 679 to 1050°F. Reversion is marked by an increase in resistivity and a decrease in hardness. It teas found that some reversion took place at all cornbinations of T1 and T2 but that pronounced rei3ersion resulfed for an Fe-18 pct Ni-5 pct Mo-8 pcl Co alloy exposed to preagz&apos;ng&apos; temperatures at or below 850°F. A similar alloy not containing cobalt exhibited no such discontinuity in reversion behazior with TI. The results are interpreted in terms of two types of molybdenum-rich precipitates, one nucleated at dislocations and the other in the matrix. The increased supersaturation resulting from the presence oj- cobalt evidently provides sufficient energy to nucleate the matrix phase. Anotnalies in the temperature dependence of the resistivity decrease and peak hurdness in the Fe-18 pct Ni-5 pct Mo-8 pct Co alloy as a junction of aging temperature noted in an earlier study are explained on this basis. SEVERAL investigatorsl-9 have studied the details of the precipitation-hardening reaction of the maraging steels. The great majority of conclusions have been drawn from transmission electron microscopy. Although much has been learned by this method, alternate techniques which will give information earlier in the aging process are needed for a more complete understanding of the series of precipitation steps probably involved in the aging reaction. Peters and cupp&apos;&apos; have recently shown, by measurements of the kinetics of precipitation, that an 18 pct Ni-Co-Mo maraging steel shows a distinct change in precipitation behavior at aging temperatures below 850°F. The results were interpreted in terms of the existence of two types of precipitates at low aging temperatures. Only one precipitate type is present at higher aging temperatures. The low-temperature precipitate was found to be a particularly effective strengthener. No evidence for the additional low-temperature precipitate was found in the 18 pct Ni-5 pct Mo ternary alloy. The object of this investigation was to study further the characteristics of the two types of precipitates and the interaction between cobalt and molybdenum characterizing this system. Some preliminary experiments indicated a difference in reversion behavior in specimens aged above and below 850°F. This suggested that knowledge of the reversion behavior might shed some light on these two questions. Hardy and Heal11 have defined reversion as the loss of hardness, electrical conductivity, or other properties caused by heating for a very short time at temperatures above the aging temperature. The precipitate reversion referred to in this paper is entirely distinct from "austenite reversion" often referred to in maraging steel literature. This latter phenomenon could more accurately be called the diffusion-controlled formation of austenite. Much has been written about reversion in several of the aluminum-base binary and ternary alloys.&apos;2-16 Two explanations for reversion have been advanced. Based on the classical nucleation theory of Volmer-Weber-Becker-Doring,17 Konobeevski18 suggested that reversion was due to the size of the precipitate particles

Jan 1, 1968

By G. Bruggeman, K. G. Kreider

Grain boundary dij]usion coefficienls were measured in tungsten between 1400° and 2200° C and can be expressed by the equation sq cm per sec This activation energy confirms some eavlier estimates made .from tungsten sintering experiments. Grain boundary diffusion was found to occur in sub-bozrndavies having -misorientations of less than 10 deg. The actiuation energy for this subboundavy diffusion is equal to that for dijjusion in incoherent grain boundaries with in the limits of error. This is shown to be consistent with the dislocation model of Low-angle boundaries wheve diffusion occlcvs along- the dislocation &apos;YPipes" comprising -tile boundary. RECENT investigations of the sintering of tungsten powders all report activation energies which are considerably less than the activation energy for tungsten volume diffusion. Kothari&apos; reports a value of 100 * 5 kcal per mole, Hayden and Brophy&apos; obtained 90 kcal per mole, and Vasilos and smith3 found 110.7 kcal per mole from their sintering studies. Since most determinations of the activation energy for volume diffu-sion4-&apos; fall between 120 and 160 kcal per mole (the true value seems most likely to be nearer 150 kcal per mole), the conclusion is drawn that the mass transport leading to densification during sintering is accomplished by grain boundary diffusion. This interpretation is consistent with various diffusion models of the sintering process. 10-12 Vasilos and Smith calculate diffusion coefficients from their data which fit the equation D * 1.36 x 10* exp(-llO,700/HD However, no direct measurements of tungsten grain boundary diffusion have been made. Furthermore, considerable disagreement exists between the directly measured values of tungsten volume diffusion.&apos;-&apos; In order to corroborate the inferred results of the sintering experiments concerning grain boundary diffusion and to provide accurate diffusion data essential to the analysis of the kinetics of creep, oxidation, precipitation, and so forth, the present work was undertaken to measure self-diffusion in single-crystal and polycrystalline tungsten between 1400" and 2200°C. It is within this temperature range that tungsten sintering is done, the re crystallization of tungsten occurs, and the widest application of tungsten as a high-temperature material will probably be made. EXPERIMENTAL PROCEDURE Radioactive WlE5 was produced by irradiating tungstic acid in a neutron flux of 1.2 x 1012 neutrons per sq cm per sec for 36 hr. A 2-week waiting period was allowed for the decay of w"~ also produced by the irradiation. (w"~ has a half-life of 24 hr.) The half-life of the remaining isotope was determined to be 75 days confirming the presence of w lE5 and the absence of any undesired radionuclide. Specimens 4 in. in diam and $ in. thick were cut from polycrystalline swaged tungsten rods (recrystal-lized) and from Linde single-crystal rods. Chemical analyses of these materials appear in Table I. Actually upon closer examination, the single-crystal specimens were found to consist of several subgrains separated primarily by tilt boundaries in which the misor-ientation ranged from 3 to 10 deg. Thus, it was possible to measure boundary diffusion coefficients in these low-angle subboundaries as well as in the incoherent boundaries of the polycrystalline specimens. The two faces of each specimen were ground flat and parallel within 0.0001 in. The radioactive tungstic acid was dissolved in concentrated ammonium hydroxide, placed on the ground flat of the specimen, and evaporated to dryness. The oxide was then reduced in hydrogen at 1000°C resulting in a layer of wlE5 approximately 1 p thick. The diffusion anneals were performed in vacuum in a tantalum resistance furnace. Time at temperature ranged from 10 hr at 1400°C to 2 hr at 2200°C. The penetration profile was determined by measuring the residual activity after successive removal of surface layers by grinding on metallographic polishing paper. Extreme care was exercised to insure that sections were always taken normal to the diffusion direction; this was verified repeatedly by checking that front and back surfaces of the specimen remained parallel. The activity was measured with an end-window Geiger-Mueller counter. The sides and edges of the specimen were well-shielded to eliminate possible effects due to surface diffusion. The weight of the

Jan 1, 1968