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By O. C. Baptist

The Umiat oil field is in Naval Petroleum Reserve No. 4 between the Brooks Range and Arctic Ocean in far-northern Alaska. The Umiat anticline has been tested by 11 wells, six of which produced oil ; however, [lie productive capacity and recoverable reserves of the field are subject to considerable speculation because of unusual reservoir conditions and because several wells appear to have been .seriously damaged during drilling and completion. Oil is produced at depths of 275 to 1,100 ft; the depth to the bottom of the permanently frozen zone varies from about 800 to 1,100 ft, .so that most of the oil reserves are in the permafrost Reservoir pressures are estimated to range from 50 to 350 psi, increasing with depth, and the small amount of gas dissolved in the oil is the major source of energy for production. Laboratory tests were made on cores under simulated permafrost conditions to estimate oil recoverable by solution-gas expansion from low saturation pressures. The cores were also tested for clay content and susceptibility to productivity impaiment by swelling clays and increased water. content if exposed to fresh water. The results indicate that oil can be produced fronz reservoir rocks in the permafrost and that substantial amounts of oil can be produced from depletion-drive reservoirs by a pre.s.r~lrr drop of as little as 100 psi below the saturation pressure. Freezing of formation water reduces oil productivity much more than that due to increased oil viscosity: Failure of we1ls drilled with rtuter-base mud to produce is attributed to freezing of water in the urea immediately surrounding the wellbore. Swelling clays apparently contributed very little to the plugging of the wells. INTRODUCTION Naval Petroleum Reserve No. 4 lies between the Brooks Range and the Arctic Ocean in northern Alaska. The Umiat oil field is located in the southeastern part of the Reserve and is about 180 miles southeast of Point Barrow (the only permanent settlement in the Reserve and the primary supply point for drilling of the wells at Umiat). Eleven wells were drilled for the U. S. Department of the Navy, Office of Naval Petroleum and Oil Shale Reserves, between 1944 and 1953 to test the oil and gas possibilities of the Umiat anticline. Six of these wells produced oil in varying quantities and the best one pumped about 400 B/D.' Estimates of recoverable oil range from 30 to 100 million bbl. The main oil-producing zones are two marine sandstone beds in the Grandstand formation of Cretaceous age: these are referred to as the upper and lower sands. Good oil shows were found throughout the sand settions in the first three wells drilled on the structure, but the highest rate of oil production obtained on any 01 the many tests was about 24 BOPD. These first wells were drilled with conventional rotary methods using water-base mud; later wells were drilled either with cablc tools using brine or rotary tools using oil or oil-base mud. These experiments were successful as is shown by comparing the oil production from Well No. 2 with that from No. 5. These two wells are only 200 ft apart and are located at about the same elevation on the structure. Well No. 2. drilled with a rotary rig using water-base mud, was abandoned as a dry hole after all formation tests were negative. Well No. 5. drilled with cable tools and reamed with a rotary using oil, pumped 400 BOPD which was the maximum capacity of the pump and less than the capacity of the well. These field results indicated that the producing sands were extremely "water sensitive" and it was assumed that the cause of this sensitivity was the presence of swelling clays in the sands. Because of the very unusual reservoir conditions and the difficulties encountered in completing oil wells in the permafrost. the Navy asked the U. S. Bureau of Mines to make laboratory studies under simulated permafrost conditions to assist them in estimating the production potential of the field and the recoverable reserves. These tests were designed to determine the cause of the plugging of wells in the permafrost and to test oil recovery from frozen sand by solution-gas expansion with the oil gas-saturated at very low pressures. EXPERIMENTAL METHODS AND PROCEDURES Samples Analyzed Core samples were analyzed that represent the lower sand in Umiat Well No. 7, the upper sand in No. 3. and both the upper and lower sands in No. 9. These sands should be productive in all of the wells because of their location on the structure. Core samples from

By E. Buehler, J. E. Kunzler

High-pu.1-ity molybdenum has been heat treated, melted, and zone refined and the physical and chemical changes that are produced by these processes have been studied by making resistance ratio measurements. Pronounced effects are observed that are associated with recrystalliza-tion at about 1200°C and with melting. Melting alone is found to result in a substantial purification by the evaporation of impurities such as iron. Zone refining is found to be reasonably effective with four passes producing a three-fold decrease in resistance ratio and a minimum ratio of 0.0003. With the aid of low temperature measurenzents, it has been shown that the build-up of a deposit of the material being zone refined on the radio frequency coil used for heating can lead to contamination of the sample. CONSIDERABLE interest in high-purity refractory metals for the study of mechanical properties has developed during recent years. Also the need for highly pure metals in certain fundamental studies, such as electronic band structure, has become quite widely appreciated. Molybdenum can now be produced with sufficiently high purity to make it attractive for such investigations. The most suitable measure of chemical purity of metals used for many of these studies is its resistance ratio, R,.,o,/Ro, During the purification of molybdenum by zone refining and its subsequent evaluation by this technique, a number of informative observations were made. These observations concern the effectiveness of zone refining, the volatilization of impurities at the melting point, and the recrystallization of molybdenum and appear to be pertinent to other refractory metals. Also, the usefulness of low-temperature resistance measurements as an analytical tool for evaluating the presence of chemical impurities and physical defects in metals is again illustrated. Samples of high-purity molybdenum of known mechanical history were heated to various temperatures between 800°c and their melting point. Resistance ratios of the samples were measured after they had been given a specified treatment. The data were used, along with mass spectrographic analysis, as an aid in interpreting the nature of the processes that occurred in conjunction with each treatment. Changes in the concentrations of chemical impurities and physical defects are typical of things that effect the low-temperature resistivity. SAMPLES The starting material was obtained from Westing-house Corp., Bloomfield, N.J. It was in the form of molybdenum rods, usually 1/8 or 3/16 in. in diameter. These had been previously processed from bars, 5/8 in, in diameter, originally reduced from 4 in. diam arc-cast ingots, by hot swaging at about 1300°c. In the final step, the temperature was lowered to about l lOO°C which resulted in the production of elongated grains. Typical grains were about 0.03 mm thick and 0.6 mm long. The molybdenum was quite pure as is indicated by the results of mass spectro-scopic analysis1 given in Column 2 of Table I. Other nongaseous elements not listed in the table were not detected. ZONE REFINING AND THERMAL TREATMENT OF SAMPLES Several sample rods, 8 to 10 in. long, were zone refined or were heat treated at several temperatures. Both types of operations were performed using 3 me-

Jan 1, 1962

By G. E. Keller, G. D. Coe

Several methods have been devised for rapid determination of sulfur in coal using a high-temperature combustion furnace. The fundamental principles of the various methods are similar but the techniques vary widely. The method described herein is no different in principle from some of its predecessors but varies considerably in technique. Originally devised to overcome the low-accuracy criticism leveled against the others, the tube-furnace method has proved successful for limited applications. Work is being done to widen the applicability of the technique. Subsequent to the work of A. Vita1 in 1920, a number of investigators have published data dealing with the rapid determination of sulfur in coal using a high-temperature combustion furnace.2-5 These, together with several unpublished methods, involve wide differences in technique although they are all similar in principle. Investigation of typical details of procedure showed that poor precision or accuracy could be attributed to one or more of the following: 1) inadequate quantity of sample to be representative, 2) a delivery tube temperature too low to confine condensation to a washable area of the tube, 3) no provision for back washing the delivery tube, 4) incomplete absorption of the sulfur compounds due to inadequate bubbler, and 5) the false assumption that all of the sulfur is evolved as sulfur dixoide. The method herein discussed is no different in principle from some of its predecessors; the differences are in technique. Although the method is rapid—a determination can be completed in 5 min— accuracy has riot been sacrificed in order to achieve speed. MATERIALS AND EXPERIMENTAL WORK Fig. 1 shows the arrangement of the equipment. A metered volume of oxygen is passed through calcium chloride for removal of moisture, then through Ascarite for removal of carbon dioxide, and thence through a glass tee to the feed end of the combustion tube. Connected to the side arm of the glass tee is a rubber tube that is closed with a pinch clamp during combustion of a sample. The products of combustion are expelled through a Vycor bubbler, the end of which is submerged 3 cm below the surface of a 1 pct hydrogen peroxide solution contained in a 300 ml high-form beaker. At the completion of the 4-min combustion period the contents of the beaker are titrated to a yellow end point, using a methyl red indicator, with 0.05 N sodium hydroxide (or sodium tetraborate). The pinch clamp on the tube leading from the tee in the oxygen line is then opened and mouth suction applied to draw the hydrogen peroxide up into the bubbler past the ell, almost to the rubber tube connecting the bubbler to the combustion tube. This washing of the bubbler is repeated until no further acid reaction with the indicator is obtained. The hydrogen peroxide-sul-furic acid solution is then titrated to the final yellow end point. Test work conducted at the Robena Laboratory disclosed the following critical conditions that had important bearing on the precision of the method: Weight of Sample: Several series of tests wherein the sample weight ranged from 0.1 to 0.5 g of -60 mesh coal showed that the lowest variance (standard deviation squared) resulted from the use of 0.5-g samples; the variance was slightly greater when 0.3-g samples were used, and with less than a 0.3-g sample weight the variance increased rapidly with decrease in weight. Although the use of a 0.5-g sample invariably resulted in a very slight explosion as soon as the sample entered the hot zone of the combustion tube, this did not detract from the precision of the method. Temperatures: Mott and Wilkinson5 found that a combination of low temperature (1250°C) and low oxygen flow rate (less than 700 ml per min) tended to give high results due to formation of oxides of nitrogen. Although the method herein employs a much higher oxygen rate than 700 ml per min, as an additional precaution to assure accurate results, 1315°C (2400° F) is recommended as the most desirable furnace temperature. The temperature of the elbow of the bubbler should be at least 75°C to minimize condensation

Jan 1, 1961

By H. M. Howe

PART I. INTRODUCTORY. § 24. INTRODUCTION.-This paper discusses the chief existing data as to the temperature, in iron-carbon alloys, of Ae.3, the upper limit of the transformation range when in equilibrium, as distinguished from Ac3, the temperature at which the end of the transformation is noted in heating up, and from Ar3, that at which its beginning is noted in cooling down. The former is in fact carried above Ae3 and the latter below Ae3 by lag. I touch incidentally on the influence of manganese on Ae3 (§ 29, p. 1102). The sections, tables, and illustrations, are numbered consecutively with those in the accompanying papers by Howe and Levy on Determination of, the Position of Ae3 in Carbon-Iron Alloys, and by Burgess, Crowe, and Rawdon on Thermal and Microscopical Examination of Professor Howe's Standard Commercial Steels, to which the present paper forms a sequel. § 25. The contradictoriness of our present evidence is shown by grouping it together in Fig. 14. For instance, both Goerens and Meyer (Series 2) and Meuthen (Series 12) used practically stationary temperature, and thus reduced the influence of lag very greatly; yet Ae3 for 0.32 carbon steel according to the former investigators is 894°, but according to Meuthen it is at or below 770°, a discrepancy of 124° or more. In view of our ability to measure these high temperatures within a few degrees, the existence of such a discrepancy is as unwelcome as it seems needless. I attack the thankless task of bringing some order out of this chaos.

Jan 6, 1913

By Freeman Bishop

Having obviously cleared the way for fast confirmation by the Senate Interior Committee, the Administration recently named Elburt F. Osborn, vice president of Penn State University, as director of the Bureau of Mines. Interior Committee Chairman Henry M. Jackson (D of Wash.) has moved hearings on the nomination right along, forecasting that they will end in a confirmation. Dr. Osborn not only made a good impression on the Committee, he also made it amply clear that he would be the boss of his job and have right-hand aides to help straighten out conflicts stemming from recently enacted health and safety regulations for miners. Mining engineers in the field hope this clarification can come soon. They are frankly fed up with local, state, regional and national overlapping of restrictions.

Jan 1, 1970

By G. E. McElroy

Much attention has been directed to mine-air flow in recent years, more especially in Great Britian where there is frequent reference to a theory of fluid flow developed by English engineers. Briefly stated, this theory is that for similar passages of the same relative roughness, in which fluid flow occurs, the conditions of flow are exactly the same for W D V equal values of the product where W = density of the fluid, D = diameter of the passage through which flow occurs, V = mean velocity of flow, and p = absolute viscosity of the fluid flowing. This, the "Reynolds Criterion" of fluid flow, had its origin in the work of Reynolds1 more than 40 years ago. Later, Rayleigh2 amplified the theory which has been conclusively proved for small pipes by the experiments of Stanton and Panne13 over a large flow range, and by Lacey4 over a somewhat more limited range. Concordant results on small pipes have also been obtained by numerous other investigators with single fluids over more or less limited ranges of flow. According to this theory, results in one medium, such as water, are immediately applicable to another, such as air; and experimental results on models are (theoretically, at least) applicable to full-scale designs. This is of great importance in aeronautics and can be of considerable value in mine ventilation research. Hodgson, in a recent paper,6 has outlined the application of this theory to mine-air flow and recent English experiments6 on the resistance of a timbered mine airway have been expressed in this form.

Jan 1, 1927

By A. E. Zawadzki

A progress report is presented on the development of a process for the removal of sulfur dioxide from flue gases. Catalytic oxidation of the sulfur dioxide in flue gases, with the production of recoverable sulfuric acid, has been demonstrated to be technically feasible. Problems associated with the process are discussed. The need for an inexpensive and efficient process for controlling sulfur dioxide emissions from utility plant stacks has been accentuated by the ever-increasing public demand for elimination of all man-made air pollutants. I would like to describe the results of an investigation of the development of such a process; more important, I would like to present a discussion of the problems associated with the process which remain to be solved. The research work on the BCR catalytic gas phase oxidation process has been jointly sponsored by the Association of Edison Illuminating Cos., Edison Electric Inst. and Bituminous Coal Research, Inc., since 1958. However, work on SO2-pollution abatement was initiated by BCR in 1953. Tieman and Clymer,1 working with ozone and simulated flue gases, evaluated a gas phase oxidation process for removing SO2 from flue gases. Their experimental data indicated that the use of ozone to oxidize SO2 in flue gas concentrations, with subsequent recovery of H2SO4, did not appear to be economical due to the large ratio of ozone to sulfuric acid produced (2.6 to 1). The cost of the ozone would be 6 to 10 times the cost of sulfuric acid produced. As a result of the ozone study, work on a catalytic oxidation process was developed. The following reactions are the basis for the catalytic oxidation process Reaction [I] normally occurs in the combustion of sulfur-bearing fuels. At the high temperature found in the combustion chamber, 95% to 99% of the sulfur in the fuel is oxidized to SO2 and 1% to 5% is oxidized to SO3. The concentration of SO2 in the combustion gases depends on the combustion efficiency and the quantity of excess air used. A commonly used rule of thumb is 0.1 percent by volume SO2 in the flue gas for each 1% sulfur in the fuel. Reaction [2] proceeds at a wide range of temperatures. The rate of the reaction is rapid above l,000°F; however, the equilibrium conversion drops rapidly above this temperature. 2 Reaction [3] occurs rapidly to completion at temperatures below 400°F; above this temperature some SO3 exists in equilibrium with H2SO4. Complete dissociation of H2SO4 occurs above 650°F.3 The simplicity of the proposed process provided added incentive to the development and evaluation of the various component unit operations. The advantages of the process were considered to be as follows: 1) no raw materials were required, 2) the unit operations were not radically new; and 3) a salable product, sulfuric acid, would be produced. The successful development of the process was contingent upon the solution of several major problems: 1) The development of a catalyst which would provide high catalytic activity at reasonable conditions of gas flow and temperature without causing an unacceptable increase in pressure drop. 2) The development of a high temperature dust collection system to provide clean flue gases to the catalytic reactor. 3) The complete recovery of the sulfuric acid produced in the process; the effluent gas must contain less than 20 ppm by volume of sulfuric acid. As of this date, the complete solution to these problems has not been achieved. EXPERIMENTAL Catalyst Development: The use of platinum and vanadium catalysts for the production of sulfuric acid by the treatment of dry gases containing 5% to 20% by volume sulfur dioxide has been known for many years. The application of the basic idea of catalytic oxidation of sulfur dioxide in flue gas concentrations was

Jan 1, 1965

By Elmer A. Jones

Development work in mines of St. Joseph Lead Co., Southeast Missouri, using trackless loading equipment shows definite advantages: Speed of cleaning, ability to work on steep grades and sharp crosscuts, good later tracking conditions, and possibility of wasting rock in old abandoned stopes. THE Desloge mine is one of a group of mines owned by the St. Joseph Lead Co., in the so-called Lead Belt of Southeast Missouri. It has been operating approximately 40 years producing a daily tonnage ranging from 1600 to 3800, depending on various factors. On an average, the present mine is 300 ft deep with an extreme extent of 2.7 miles by 1.7 miles. Most of the present mining is in the lower horizons of the Bonne Terre dolomite, a fairly soft rock requiring no support except occasional channel iron and roof pins. Due to the contour of the underlying sandstone and porphyry, some development work has been through short stretches of these different formations. In some areas the lower part of the dolomite is quite sandy and generally is considered abrasive. Sizes and Methods of Drifting Have Changed: Development work has, like other phases of mining, changed considerably in the last 20 years, from cleaning by hand to the use of a mechanical method. The conception of a standard drift has also changed. Before the advent of mechanical loading in stopes there were many pieces of main line drift averaging 7 ft high x 9 ft wide. With the coming of the St. Joe shovel the drift was increased to 8 ft high x 10 ft ELMER A. JONES, Member AIME, is Assistant General Mine Superintendent, St. Joseph Lead Co., Bonne Terre, Mo. AIME Columbus Meeting, September 1949. TP 2859 A. Discussion (2 copies) may be sent to Transactions AIME before July 31, 1950. Manuscript received Sept. 16, 1949. wide. Now with the Joy loader and shuttle car, a 9x11 ft drift is coming to be standard size. Methods of cutting drifts have changed considerably over the last few years. Some changes in drilling equipment have been made such as reducing the weight of column, clamp, air feed, and fittings to go with the HC10 Cleveland jackhamer. Other changes have been made in drill steel such as the use of detachable bits; throw-away variety, screw type, and the tungsten-carbide insert bits. Later developments have introduced spiral-welded pipe with victaulic couplings, millisecond exploders, bulky powder, and the use of electric cap lamps. Experimental work is going on continually in various phases of development work, some to be tried and discarded, others gradually to become standard practice. To sum up, the standard method of development now in use at Desloge is as follows: The work is done on a two-shift cycle 7:00 p.m. to 3:00 a.m. and 7:00 a.m. to 3:00 p.m. Two men known as development drillers comprise a crew on each shift. These two men arrive at their work about 7:30 to find a round blasted by the previous shift. After scaling down back and walls they proceed to the cleaning operation, using either a Joy loader and shuttle car, a drag hoist mounted on a slide ramp, or an Eimco Finlay to load into a 21/2 ton mine car. Cleaning may take from 2 to 4 hr depending on conditions such as length of round broken, length of haul, and other variables. After fitting up pipe and setting up columns and drills they are ready to drill a round which should measure 9 ft high x 11 ft wide and break from 5 to 7 ft advance. This may also take from 2 to 3 hr. Then they are ready to charge and

Jan 1, 1951

By Elmer A. Jones

Development work in mines of St. Joseph Lead Co., Southeast Missouri, using trackless loading equipment shows definite advantages: Speed of cleaning, ability to work on steep grades and sharp crosscuts, good later tracking conditions, and possibility of wasting rock in old abandoned stopes. THE Desloge mine is one of a group of mines owned by the St. Joseph Lead Co., in the so-called Lead Belt of Southeast Missouri. It has been operating approximately 40 years producing a daily tonnage ranging from 1600 to 3800, depending on various factors. On an average, the present mine is 300 ft deep with an extreme extent of 2.7 miles by 1.7 miles. Most of the present mining is in the lower horizons of the Bonne Terre dolomite, a fairly soft rock requiring no support except occasional channel iron and roof pins. Due to the contour of the underlying sandstone and porphyry, some development work has been through short stretches of these different formations. In some areas the lower part of the dolomite is quite sandy and generally is considered abrasive. Sizes and Methods of Drifting Have Changed: Development work has, like other phases of mining, changed considerably in the last 20 years, from cleaning by hand to the use of a mechanical method. The conception of a standard drift has also changed. Before the advent of mechanical loading in stopes there were many pieces of main line drift averaging 7 ft high x 9 ft wide. With the coming of the St. Joe shovel the drift was increased to 8 ft high x 10 ft ELMER A. JONES, Member AIME, is Assistant General Mine Superintendent, St. Joseph Lead Co., Bonne Terre, Mo. AIME Columbus Meeting, September 1949. TP 2859 A. Discussion (2 copies) may be sent to Transactions AIME before July 31, 1950. Manuscript received Sept. 16, 1949. wide. Now with the Joy loader and shuttle car, a 9x11 ft drift is coming to be standard size. Methods of cutting drifts have changed considerably over the last few years. Some changes in drilling equipment have been made such as reducing the weight of column, clamp, air feed, and fittings to go with the HC10 Cleveland jackhamer. Other changes have been made in drill steel such as the use of detachable bits; throw-away variety, screw type, and the tungsten-carbide insert bits. Later developments have introduced spiral-welded pipe with victaulic couplings, millisecond exploders, bulky powder, and the use of electric cap lamps. Experimental work is going on continually in various phases of development work, some to be tried and discarded, others gradually to become standard practice. To sum up, the standard method of development now in use at Desloge is as follows: The work is done on a two-shift cycle 7:00 p.m. to 3:00 a.m. and 7:00 a.m. to 3:00 p.m. Two men known as development drillers comprise a crew on each shift. These two men arrive at their work about 7:30 to find a round blasted by the previous shift. After scaling down back and walls they proceed to the cleaning operation, using either a Joy loader and shuttle car, a drag hoist mounted on a slide ramp, or an Eimco Finlay to load into a 21/2 ton mine car. Cleaning may take from 2 to 4 hr depending on conditions such as length of round broken, length of haul, and other variables. After fitting up pipe and setting up columns and drills they are ready to drill a round which should measure 9 ft high x 11 ft wide and break from 5 to 7 ft advance. This may also take from 2 to 3 hr. Then they are ready to charge and

Jan 1, 1951

By H. C. Chang, N. J. Grant

Creep of very coarse grained, high purity aluminum was studied at 400° to 1100°F with an initial stress range of 50 to 1200 psi. The process of boundary sliding and migration was studied. The driving force of boundary migration under creep conditions is shown to be a combination of strain energy migrationand surface energy. A theory is presented regarding the strainenergyrole the grain boundaries play under creep conditions. From this thetheory intercrystalline failure of commercial alloys can be explained. Also from this theory an optimum grain size should exist for good high temperature properties of high purity materials. IN the investigation of the creep of very coarse grained, high purity aluminum previously reported,' the cyclic nature of the process of grain boundary sliding and migration has been established by microscopic observation of the actual creep process as well as metallographically. It was also substantiated by measuring localized strains across the grain boundaries. In addition, it was shown how extensive subgrain and fold formation may result from boundary sliding and how the slid grain boundary may become sharply wavy as a result of subgrain formation. Since the publication of those results, additional information on the process of grain boundary sliding and migration has been obtained. It is the purpose of this paper to report on the direction and driving force of boundary sliding and migration, the effect of grain size, and the effect of temperature. Finally the effect of decreasing purity (alloys 2s and 3s) on the process of boundary sliding and migration is noted. From these results, an explanation is presented for the intercrystalline failure of alloys under creep conditions. The effects of grain size on the creep properties of impure and high purity materials are discussed in the same light. The experimental procedures and technique have been presented elsewhere.' It is only necessary to state how the 2s and 3s aluminum specimens are prepared. Machined specimens were first annealed at 600°F for about 12 hr. In order to produce a large grain size the specimens were then stretched 3 to 8 pct. The specimens were marked with reference marks, electropolished, annealed at 900°F for 24 hr and at 1150°F for 12 hr, and repolished. The grain size of 2s aluminum produced by this treatment is comparable to that of high purity aluminum in the direction of its width of the specimen, i.e., there are 2 to 4 grains across the width of the specimen. However, the grains of 2s aluminum are 3 to 10 times longer in the direction of the specimen axis. On the other hand, the grain size of coarse grained 3s aluminum ranges from 10 to 20 grains across the width of the specimen due to the treatment just outlined and therefore is much smaller than that of both high purity and 2s aluminum. As in 2s aluminum, the grains are about 3 to 10 times longer in the direction of the specimen axis than in the direction of the width of the specimen. The arrangements of the grains in 2s and 3s aluminum were generally irregular; therefore it was difficult to follow the course of the grain boundaries. Results Method of Presentation: In order to show the arrangement of the grains, especially the direction and positions of the grain boundaries, traces of the grain boundaries on the four surfaces of the specimens were unfolded and mapped out after macroetching. Figs. 1 and 2 show the structural development drawings of specimens P-3 and P-8 respectively. The two flat surfaces (of which the front one faces the microscope) and the round-edged surfaces will be called the "front surface" and "back surface" and

Jan 1, 1954

By S. R. B. Cooke, H. S. Choi, D. H. Harraway, I. Iwasaki

The mineralogy of natural iron ore samples and their slimes have been investigated and the nature of slime interference in iron ore flotation has been studied. The results have been correlated with the flotation behavior of a natural ore sample. Various conclusions have been reached as a result of these studies. In the flotation of iron oxide ores, desliming is generally considered to be an essential step to successful separation, irrespective of whether the iron oxide or siliceous gangue minerals are to be floated, although some workers have found empirically that certain collectors and reagent combinations are less sensitive to the presence of slime than others. The detrimental effect of slime is considered to be twofold. First, the presence of slime presupposes a high reagent consumption because of high specific surface. When clays are present and when cationic collectors are used abstraction by ionic exchange may augment this condition. Attempts to compensate by the addition of large amounts of reagent result in only partial correction. Second, slime coatings on granular particles tend to interfere with the bubble-mineral contact. The nature of slime coatings in flotation is quite complex and has been the subject of considerable study; an attempt was recently made by Fuerstenau et al.' to relate the slime-coating density with flotation recovery and with the properties of the electrical double layer at the mineral surfaces. Although major constituent minerals in the oxidized iron ores of the Mesabi and Cuyuna ranges are hematite and goethite (limonite) as the iron oxides, and quartz and chert as the siliceous gangue, very little is known of the mineralogy and of the chemical and physical characteristics of the slimes, and still less of the interaction between slimes, collector, and the mineral surfaces. For pragmatic reasons iron ore slimes are defined as — 20p material, based upon the calculated settling velocity of a quartz sphere of the stated diameter, and of all other equal-settling mineral particles. Active slime interference with flotation is usually attributed to particles 5p in size or finer, the extent of such interference appearing to depend not only on the mineralogy but also on the size distribution of each mineral in the slime fraction. The objective of this work was to acquire a more specific knowledge of the constitution of iron ore slimes and of their role in flotation. The mineralogi-cal composition of natural slimes was obtained by differential thernal analysis (hereinafter referred to as DTA), electron microscopy, and chemical and X-ray analyses. Some flotation tests were made on natural ore samples. The surface properties of several constituent minerals were investigated by electrophoretic measurements and by determination of the adsorption of some typical flotation collectors. Finally, simplified flotation tests were made on granular goethite and quartz in the presence of various artifically prepared slimes; the results were compared with laboratory flotation tests made on natural ores. MATERIAL AND METHODS Mineralogy of Some Iron Ore Slimes: Samples of two wash-ore tailing::, hereinafter identified as A* and B, *Sample A of the present investigation 18 the same am ore A in ref. 3. of a wash ore C, and of a paint rock D, all from the Mesabi range, were selected for investigation on the basis of prior information concerning their flotation behavior. The two wash-ore tailings, when deslimed, were known to respond well to flotation, whereas the wash ore was high in goethite, tended to be slimy, and responded poorly to flotation. The paint rock also exhibited sliming tendencies, and was suspected to contain relatively large quantities of clay minerals because of its high A1203 content. Gruner states that the paint rock of the Mesabi frequently contains kaolinite. To ascertain the relative sliming tendencies of each sample a standardized desliming method was employed. All samples were ground through 65 mesh using jaw and rolls crushers. A 500-g sample of each

Jan 1, 1962

By D. A. Stevenson, T. Alden, J. Wulff

A portion of the liquidus curve has been determined for the binary alloy systems Ni-Pb and Cr-Pb. The solubility of nickel is 0.53 atomic pet at 372° and 18.63 atomic pet at 1200°C. Chromium shows low solubility, 0.634 atomic pet at 1210°C. Molybdenum and tungsten were also studied and found insoluble in lead, less than 0.005 atomic pet at 1200°C. INCREASED use of liquid metals of low melting X point for heat transfer, coating, joining, and other purposes has renewed interest in the solubility of structural metals in these liquids. A study of Hansen1 and current literature indicates that few liquidus curves at the low melting end of the binary diagrams have been accurately delineated. This statement applies particularly to the binaries of lead. The present paper is limited to nickel, chromium, tungsten, and molybdenum in lead. In early studies2, 3 of the lead end of the Pb-Ni system, a monotectic at 1340°C was established. Tammann and Oelsen' determined the solid solubility of nickel in lead at 20°C to be 0.023 wt pet. Recently Pelzel5 determined the liquidus curve from the eutectic temperature of 327° up to 727°C using a segregation method. In the present paper this part of the curve has been checked and extended to 1244°C. The Pb-Cr system was first studied by Hindrichs.6 He pointed out the existence of a monotectic at 1470°C and indicated a tentative liquidus. Recent corrosion studies of Fe-Cr alloys in lead suggest that chromium is more soluble than iron in lead.7-8 The solubility of tungsten in lead according to Inouye8 is about 30 wt pet at 1200°C. Appreciable solubility of molybdenum in lead might therefore be expected. Experimental Various experimental techniques have been employed in the determination of solubility in liquid metals. For low solubility, thermal analysis is unsatisfactory. A segregation method was used by Pelzel3 in his study of the Pb-Ni system. In this procedure separation of liquid and solid is possible due to difference in density. In the technique of Kleppa10 a single piece of material is maintained in contact with the liquid metal in evacuated Vycor vials. After equilibration, solid and liquid are separated by tilting. Keck and Broder" measured the weight of a piece of the solid solute before and after immersion in a pure solvent bath; the weight loss was a measure of the solubility. All of the above procedures are time-consuming since they permit only one determination per run. Numerous samples for analysis may be taken from the melt in the method described by Gurinsky and CO-workers.10 The rate of extraction of samples is limited only by the time required for equilibration. In the present work, a modification of this method was employed. A 150-g charge of analytical reagent grade lead and the added metal* were contained in an Alun- dum crucible. It rested on firiely divided silica at the closed end of a 45 mm Vycor tube, 500 mm long. The top of the tube was provided with an inlet and

Jan 1, 1959

By P. A. Flinn

ALTHOUGH many physical properties of superlat-tices have been studied intensively, relatively little attention has been paid to their mechanical properties until recently. Even for the well-known transformation in 0 brass, the effect of the transformation on plastic behavior has only lately been extensively investigated.''' A partial analysis of dislocation structure in superlattices has been given by cottrel13 and his theory agrees well with the experimental results on CU3AU.4,5 His analysis, however, is implicitly limited to low-temperature effects, since it does not include the behavior of dislocations at temperatures high enough for diffusion, and hence climb, to occur. The work of Herman and Brown2 on the creep of 0 brass indicates that important effects occur under such conditions, and consequently, the theory should be extended to include them. Such high-temperature effects cannot be observed in Cu3Au, since it disorders below the temperature at which diffusion occurs at a reasonable rate. There are materials of the same structure, however, such as Ni3A1, which retain their order up to, or close to, the melting point. GEOMETRY OF THE COMMON SUPERLATTICES The two best-known ordered structures are the 0 brass type, B2, shown in Fig. 1, and the Cu3Au type, Ll2, shown in Fig. 2. In the B2 structure the (000) and (1/2, 1/2, 1/2) sites are different in that they are occupied by different types of atoms. The symmetry of the structure is then lowered from a body-centered cubic, A2, in which the sites are equivalent, with atoms located randomly in the sites, to simple cubic. This lowering of symmetry has the consequence that two types of regions may occur within a crystal: regions where A atoms are in the (0, 0, 0) sites, and regions where they are in (1/2, 1/2, 1/2) sites. The boundary between two such regions will contain bonds between like atoms, and be a surface of higher energy. These regions are known as antiphase domains and the boundary as antiphase boundary. In the B2 structure, boundary formed during the ordering process should disappear as a result of domain growth, since any domain growing to the boundary of two others will join one and engulf the other.' In any well annealed crystal, only a single domain should exist, with antiphase boundary present only in connection with dislocations, as discussed below. The L1, structure is related to the A1 (face-centered cubic) in much the same way as the B2 is to the A2. The face-center sites are occupied by A atoms, and the corner sites by B atoms. The symmetry is again lowered to simple cubic, and antiphase domains can exist. In this case, however, there are four initially equivalent sites in the unit cell: (0,0,0), (0, 1/2, 1/2), (1/2,0, 1/2) and (1/2, 1/2, 0). In the ordered structure any one may be occupied by a B atom and the other three by A atoms. Thus four types of antiphase domains can occur in this structure. This is sufficient to permit a metastable "foam structure" to exist within a crystal.''7 Antiphase boundaries along three different planes are shown in Figs. 3, 4, and 5.* *The presence of a layer of disordered material between antiphase domains, as suggested by Jones and Sykes8 does not seem likely. Such a layer would be a region of unnecessarily high energy which could readily be reduced by the formation of the type of boundary discussed here.__________________________________________________________ The notation (111) [110] means a boundary lying along a (111) plane between antiphase regions related by a 1/2 [I10] translation. It may be seen in Figs. 3 and 4 that an antiphase boundary usually results in incorrect nearest neighbors (shown connected by braces). However, as pointed out by Wilson, a boundary of the (001) [I101 type can exist

Jan 1, 1961

By R. D. Pehlke, J. V. Gluck

The limiting activity coefficient of zinc in a "binary " solvent has been described for several dilute ternary solutions by combining literature data from recent interaction studies in the terminal regions with thermodynamic data for the central regions. Results are discussed in terms of the Alcock and Richardson random solution model. The observed behavior agrees semiquantitatively with predictions using the model. RECENT efforts in the thermodynamics of dilute ternary liquid metallic solutions have been mainly concerned with the interactions between two dilute solutes, that is, the terminal region at an apex of the composition diagram.'-' A more general case is that of the behavior of a dilute solute over the full range of a ternary system, or, more specifically, the limiting activity of solute i as projected to the k-j binary side of the i-j-k composition triangle. An implication of this is that the interaction between i and j at the k apex should connect in some way to the interaction between i and k at the j apex. A model to characterize various types of expected behavior has been discussed by Alcock and Richardson.9,10 Such behavior can range from a simple linear relation for In yi over the 1-k binary to more complex curved relations which depend on various assumptions regarding the heat of solution in the j-k binary system and the presence or absence of clustering with solute i. Quantitative data to assess these concepts have been limited primarily to the cases of nonmetallic interstitial solutes in ferrous solutions. Alcock, Richardson, and various coworkers9-13 have discussed the behavior of oxygen, sulfur, silicon, or hydrogen in dilute solution over the range of iron + metal systems; however, the only data considered by them for substitutional nonferrous metallic solutions were the results of Elliott and Chipman concerning the activity of cadmium in the Pb + Sn, Pb + Bi, and Pb + Sb systems.9 These data were limited and did not cover the terminal regions in detail. An opportunity to extend the Alcock and Richardson considerations to the dilute solution of zinc in various "binary" solvents has been afforded by combining results of several of the recent investigations of ter-minal-region interactions with previous data from the literature for the same more concentrated solutions. RESULTS AND DISCUSSION The results of the analysis are shown in Figs. 1 to 5 where the log activity coefficient, (In yZn)xzn--o, is plotted vs the composition of the "binary" solvent. In these plots the end points are the values for In yzn in the appropriate binary solution with Bi, Pb, Sn, Cd, or In at the indicated temperature—usually 550°C (823°K). For the terminal regions the slopes were drawn using the first-order interaction parameters taken from various studies reported in the literature. The data points shown in the central regions were obtained by the short extrapolation to infinite dilution of the logarithm of the activity coefficient calculated from thermodynamic studies reported in the literature for the same systems. The sources of the data are indicated on each figure. Second-order effects were not considered. Reasonably smooth curves can be drawn to connect the central region with the terminal regions for the Zn-Pb + Bi system, Fig. 1, the Zn-Pb + Zn system, Fig. 1, and the Zn-Bi + Cd and Zn-Bi + Sn systems, Fig. 2. As shown in Fig. 2, where central region data are available from two independent investigations, the agreement is quite good. The Zn-Pb + Cd system does not appear to be as well behaved as the previous four, Fig. 3; however, this type of behavior has also been

Jan 1, 1970

By W. Shockley

THIS lecture can best begin with a statement of the chief conclusion: The metallurgical industry will find profit in supporting fundamental research on dislocations. This support should be done both in their own laboratories and in universities. My lecture consists of an exposition of the basis for this conclusion. The experience on which I base it is drawn largely from two fields in solid state physics—one field is transistor electronics and the other is dislocation theory. At present the relationship of solid state physics to technology is different in these two fields. In electronics without question, the physics has led the technology. In metallurgy, on the other hand, the technology in the form of metallurgical art is far ahead of the fundamental science. In transistor electronics, physics has suggested and can still suggest previously unachieved combinations of matter that will have new and useful properties; that is, the physicist can make specific predictions. The physicist can also have some confidence that the predicted devices will actually come into existence in a matter of months or years and that they will live up to the predictions. In metallurgy, the physicist cannot to a comparable degree make predictions and have the same hope that they will lead to something new and valuable. There are a number of reasons for this difference. The first is simply historical. Transistor physics is young. It may be regarded as dating from the announcement of the transistor, in which case it is about four years old, or from the first real control of semiconductors as materials (this was accomplished largely by metallurgists, by the way) in which case it is about ten years old. Metallurgical art, on the other hand, is thousands of years old. There is no doubt that the advance of this art has been and will be hastened by a good fundamental understanding of the quantum theory of atomic phenomena. It, is too much to expect, however, that theory will soon catch up with the lead that practice has gained in a thousand years, and that theory will then point out specific pathways to better materials. It seems more probable that modern atomic theory will serve to interpret and organize information much as thermodynamics has done through phase diagrams. In this lecture, I shall emphasize an important feature common to both solid state electronics and to metallurgy. This common feature is the harmonizing principle that justifies discussing electronics and metallurgy as related topics in solid state physics. In both cases the important properties of the materials arise from imperfections. By imper- fections I mean deviations of the materials from perfect single crystals. The imperfections may be of many forms. From the point of view of utility they may be either good or bad, and a given type may be good or bad depending on circumstances. The technical material of my lecture will be divided into two parts. The first will be chiefly concerned with four types of imperfections in germanium crystals. The control of these imperfections makes possible the fabrication of useful electronic devices. A good example of such control is the junction transistor, which I shall discuss from this viewpoint later. The junction transistor, as some of you may have heard, can be used as an amplifier of electrical signals and in a number of respects surpasses what has hitherto been achieved with vacuum tubes. The second part of my technical material will be concerned with dislocations. For about fifteen years the theoretical physicist has had dislocations in mind as the most important kind of imperfection in metals. He has, however, until recently had experimental material of a highly speculative nature to back up his assertions. I am fortunate in the timing of this lecture to be able to describe some recent results that put dislocations on a far more definite basis than has been the case in the past. In fact there are now some experiments which reveal the characteristic properties of dislocations almost as clearly as experiments in transistor physics reveal the properties of holes and electrons, properties that I shall soon describe. It is this advance in the status of dislocations that emboldened me to make my initial assertion that the metallurgical industry will profit from supporting fundamental research on dislocations. Transistor Electronics In order to discuss imperfections in semiconductors, it is necessary to visualize a reference condition that may be regarded as perfect. In the cases of silicon and germanium, which find application in transistor electronics,' the perfect structure is the diamond structure shown in Fig. I. In this structure, each atom is surrounded by four neighbors with which it forms four covalent or electron-pair bonds. These bonds use all of the four valence electrons possessed by each of the silicon or germanium atoms. The electronic structure of the crystal is thus complete and perfect. A crystal of silicon or germanium with a perfect electron-pair bond structure would be an insulator, In order for electrical conduction to occur, it is necessary for imperfections to arise in the electronic structure. In this lecture, I shall discuss four possible imperfections whose symbols and relationships are indicated in Table I. We shall consider first, as an example, a crystal of silicon containing an arsenic atom as an impurity.

Jan 1, 1953

By Reed W. Hyde

SOME information has been published on the sulphur dioxide concentration of gases from Dwight-Lloyd machines sintering lead ores but most of this relates to the customary practice in which the charge is relatively high in lead and is sintered in two passes over the machine. It is thought, therefore, that the following observations on sintering in one pass a low-lead, low-sulphur charge may be of interest. The data were obtained in sintering lead sulphide flotation concentrates mixed with minus 20-mesh oxide ore, the mixture carrying 16.8 per cent Pb and 5.3 per cent S. No returns were used because of the limited amount of sulphur available as fuel, but the mixture pelletized readily to make a satisfactorily permeable bed on the sintering machine. As there was a possibility that the SO2 might be utilized, a series of runs was made to determine the concentration of S02 in the gases at different points along the wind box, and the effect on this concentration of changes in the wind-box vacuum. Several runs each were made with vacuums (as measured in inches of water at the wind box) of (1) 2 to 1 1/3 in., (2) 4 to 3 1/2 in. and (3) 6 to 5 1/8 in. The averages of the determinations from each series are platted on the graph (Fig. I). The vertical scale shows the percentage by volume of SO2 (as determined by the Reich method), and the horizontal scale shows the time expressed as percentage of the total sintering time. Sintering was considered to be complete when no S02 could be detected in the gases. In all cases the depth of bed was 4 ½ in. and the weight of dry charge per square foot of hearth area was 45.2 lb. Other data are given in the table. The volume of gases corresponding to the several points along the wind box at which S02 determinations were made could not be measured, but has been calculated from the S02 content and sulphur elimination on the assumption that the volume is uniform throughout the sintering period. This is not strictly true, as with a given vacuum the volume will usually drop slightly toward the middle of the period and increase toward the end. However, this assumption is a reasonable approximation. Several interesting features are brought out by these data. In general, the published data on S02 concentration in sintering under ordinary conditions show a high S02 concentration in the early stages followed by a rapid decrease in concentration and with relatively little SO2 in the gases from the last half or third of the operation. In other words, the greater part of the sulphur elimination is obtained in the first third or half of the period. In these runs, the 6-in. vacuum, which approximates the usual operating condition, gives a curve that follows this customary pattern. Maximum S02 concentration is obtained 2 ½ min. after

Jan 1, 1942

By K. G. Davis, P. Fryzuk

The diffusivity of silver in liquid tin has been determined, using the capillavy-reservoir technique, over the temperature range 250° to 500°C. The new value, D = 2.5 x 10'* exp(-2480/ RT) sq cm per sec, differs from that obtained by other workers in an earlier investigation. The analysis of data from the capillary-reservoir technique is discussed. In a recent investigation of the solidification of dilute alloys, values for the diffusion constant of silver in liquid tin were required in the analysis of the formation of impurity substructures. AS a result, measurements were made of the diffusion constants in the temperature range 250° to 500°C (melting point of tin 232°C), for the alloy concentrations used in the solidification experiments and at higher concentrations, to verify previous determinations.I)2 The capillary-reservoir method was adopted, using experimental procedures similar to those followed by Ma and Swalin,1 with the main exception that radioactive silver was used in the present investigation to facilitate solute-concentration measurements. EXPERIMENTAL PROCEDURE a) 100 ppm Samples. Glass capillary tubes of 2 mm inside diameter and approximately 5 cm- long were sealed at one end, evacuated, and filled with tin of 99.999 pct purity. The region of shrinkage near the mouth was cut off, and the tubes were then placed in a graphite holder and immersed, with the open end up, in an unstirred bath of alloy containing 100 ppm Ag 110, where they remained for periods of up to 30 hr. On removal from the bath they were cooled by an air blower. The bath was kept under a small positive pressure of argon, and the temperature controlled to within +1°C. A 10-hr diffusion period was used in the majority of the tests, scatter on runs of less than 5 hr being rather large. The procedure outlined above was chosen in preference to putting alloy in the capillary and pure tin in the bath, in order to avoid segregation when the tubes filled with alloy were first solidified. To minimize segregation when the diffusion period was complete and the capillaries again solidified, the earlier samples were held in thin-walled silica tubes which could be cooled very rapidly. Later tests were made in precision-bore Pyrex tubes, to eliminate effects caused by variations in the capillary diameter. No consistent differences in diffusivity as measured in the two types of tube were detected. After removal from the glass tubing, the samples were sectioned into 2.5 mm lengths and counted for y activity, using a scintillation counter with fixed geometry. Samples were also drawn directly from the bath and counted, so that values for C/C,, the ratio of the weight of Ag 110 in the sample to that in the bath, could be obtained. b) 5000 ppm Alloy. To check for possible effects of concentration, the silver content of the bath was increased to 5000 ppm. Complete mixing was found to have taken place in the capillary after a 10-hr period at 300°C. It appears that the greater density of the alloy was sufficient for buoyancy forces to cause instability in the alloy-tin interface, leading to rapid convective mixing. For the 5000 ppm alloy, therefore, the bath was of pure tin and the capillary tube was filled with alloy. With this arrangement, values of D consistent with those for the 100 ppm alloy were obtained, Fig. 1. CALCULATIONS OF DIFFUSIVITY The terminology used applies to a capillary of pure tin immersed in a bath of alloy. 1) Error-Function Method. under the present experimental conditions, the rod of liquid tin into which silver is penetrating may be considered semi-infinite. Assuming the concentration at the mouth of the tube to remain constant at Co, the concentration C at distance x from the mouth of the tube at time / is given by3 Plots of the inverse error function of (1 -C/Co) vs .v gave straight lines passing through the origin with slope 1/2-, x being corrected for shrinkage both on solidification and while cooling to the melting point (total correction about 6 pct at 500°C). Values for log D obtained in this manner are shown in Fig. 1. A least-squares fit to the relation D = Do exp(-Q/RT)

Jan 1, 1965

By Reed W. Hyde

SOME information has been published on the sulphur dioxide concentration of gases from Dwight-Lloyd machines sintering lead ores but most of this relates to the customary practice in which the charge is relatively high in lead and is sintered in two passes over the machine. It is thought, therefore, that the following observations on sintering in one pass a low-lead, low-sulphur charge may be of interest. The data were obtained in sintering lead sulphide flotation concentrates mixed with minus 20-mesh oxide ore, the mixture carrying 16.8 per cent Pb and 5.3 per cent S. No returns were used because of the limited amount of sulphur available as fuel, but the mixture pelletized readily to make a satisfactorily permeable bed on the sintering machine. As there was a possibility that the SO2 might be utilized, a series of runs was made to determine the concentration of SO2 in the gases at different points along the wind box, and the effect on this concentration of changes in the wind-box vacuum. Several runs each were made with vacuums (as measured in inches of water at the wind box) of (1) 2 to 1 3/4 in., (2) 4 to 3 1/2 in. and (3) 6 to 5 1/8 in. The averages of the determinations from each series are platted on the graph (Fig. I). The vertical scale shows the percentage by volume of SO2 (as determined by the Reich method), and the horizontal scale shows the time expressed as percentage of the total sintering time. Sintering was considered to be complete when no SO2 could be detected in the gases. In all cases the depth of bed was 4 1/2 in. and the weight of dry charge per square foot of hearth area was 45.2 lb. Other data are given in the table. The volume of gases corresponding to the several points along the wind box at which SO2 determinations were made could not be measured, but has been calculated from the SO2 content and sulphur elimination on the assumption that the volume is uniform throughout the sintering period. This is not strictly true, as with a given vacuum the volume will usually drop slightly toward the middle of the period and increase toward the end. However, this assumption is a reasonable approximation. Several interesting features are brought out by these data. In general, the published data on SO2 concentration in sintering under ordinary conditions show a high SO2 concentration in the early stages followed by a rapid decrease in concentration and with relatively little SO2 in the gases from the last half or third of the operation. In other words, the greater part of the sulphur elimination is obtained in the first third or half of the period. In these runs, the 6-in. vacuum, which approximates the usual operating condition, gives a curve that follows this customary pattern. Maximum SO2 concentration is obtained 2 ½ min. after

Jan 1, 1942

By Charles C. Fatino, Joel S. Hirschhorn

Loose compacts of strained and annealed stainless-steel powders were sintered at various temperatures and times to determine the effect of residual strains on the sintering behavior. The atomized powders were prepared by annealing, ball milling, and rean-nealing. The residual strains and domain size were determined by a Fourier analysis of X-ray diffvaction dala. The specimens were prepared by siwzultaneously sintering cylinders of both strained and unstrained powder. The evaluation of the sintered compacts included density measurements, metallographic examinations, and analyses of X- ray diffraction data. The results of these studies reveal a definite increase in sintered density and sintering rate for the strained powders. THE pressure compacting of metal powders causes deformation of the particles, mechanical interlocking, and increased contact area. After the deformation, severe residual strains remain in these particles. The subsequent contributions of these strains to the sintering process have been considered to be negligible, since the recovery and recrystallization temperatures usually occur prior to the temperature required for the sintering process. Sintering is con-sidered to be the process by which the powders are transformed into solid compacts at temperatures below their melting points. The sintering operation for stainless steel usually takes place in the range of 2050" to 2400°F (0.84 to 0.95 T,, where T, is the absolute melting point or liquidus temperature) while the temperature required for recovery is approximately 1800°F (0.75 T,). However, it has been shown for several metal powders that densification becomes significant in the range of 0.35 to 0.45 T,.' It is the purpose of this study to determine what effect residual strains have upon the sintering behavior of stainless-steel compacts. Loose compacts were selected for study in order to isolate the strain contributions and eliminate the variables inherent in sintering of pressure-formed compacts. Additional variables were minimized by using only one mesh size, one composition, one particle shape, and also by simultaneously sintering both types of powder. Very little work has been carried out previous to the present study to delineate the effect of strains on sintering behavior. Lenel et 01.2 observed that residual stresses in copper compacts caused shrinkage at comparatively low temperatures. Delisle3 loose-sintered ball-milled electrolytic iron and observed that bonding among particles began at a lower temperature as compared to the behavior of annealed powder. Increased densification of ball-milled oxide powders has also been noted.4'5 EXPERIMENTAL PROCEDURES Powder Preparation. The powder used for this study was a commercial-type 316L stainless steel made by the atomization process. A typical chemical analysis is: C- 0.025 pct Mo- 2.2 pct Cr-18.6 pct Ni-12.5 pct Fe—Balance The atomizing process is essentially the rapid freezing of liquid droplets. This nonequilibrium cooling causes coring to occur and two distinct phases are present within the solid particle, the austenitic phase and the ferritic phase. Due to the presence of this ferritic phase, the particles tended to fracture as well as become cold-worked during the subsequent ball-milling operation. (It was also found that this type of cooling produced a broadened and shifted

Jan 1, 1968

By T. E. Scott, R. P. Zerwekh

The charactevistics of the deformatiotz of fcc thorium were examined between 78 and 473 K. Activation energy, actiuation volume, and the temperature dependence of the flow stress were determined and conlpared uith several theories for the rate-controlling mechnnistn of the tempemture-dependent component of the flou~ stress. It was established that the Cottrell-Stokes law does not hold, even approximately, for thorium. Through consideration of the above factors and other parameters, it was concluded that the vandom solute barrier theory proposed by Friedel demonstrates the best agreement with experimental observations of the deformation of thorium below ambient temperature. THORIUM, the first metal in the actinide series of rare-earth elements, is interesting and important from two points of view. In the more practical vein, it is a potential reactor fuel. As such, it is important to know its properties. Of specific interest here are the mechanical properties of thorium. Second, no detailed information concerning the deformation characteristics of the actinide elements has been gathered to date. In view of the interesting physical and chemical properties of these metals, their mechanical behavior might reveal characteristics which could improve our understanding of the mechanisms controlling deformation of the more common metals. For example, it has been shown1 that thorium exhibits a yield point which is greatly enhanced by interstitial solute elements such as carbon. This is not a normal occurrence in fcc metals. The goal of this investigation, therefore, was to characterize the deformation of polycrystalline thorium. MATERIAL AND PROCEDURES Thorium, made by the magnesium intermediate alloy process described by Peterson et al.,2 was rolled and swaged to 0.065-in.-diam wire. The metal analysis is given in Table I. After preparation, the oxygen and nitrogen contents had risen to 308 and 60 ppm, respectively. The 0.065-in.-diam wires were cut into 2-in. lengths and annealed in a vacuum of lo-' Torr at 750°C for 1 hr, producing a grain size of 2735 grains per sq mm. The ends of the 2-in. sections were masked off so that a 1-in. gage length could be electropolished. Specimens were polished at 35 v in a solution of 6 pct perchloric acid in methanol which was maintained at 0°C . The gage diameters after polishing were about 0.0625 in. The tests were run on a screw-driven tensile machine at a constant crosshead speed corresponding to a strain rate of 0.005 min-'. The strain rate was changed rapidly after each 0.01-in. extension between 0.005 min-' and one of three higher strain rates which were selected in order to achieve strain-rate ratios of 5, 10, and 20. Tests were run at several temperatures from 78" to 473°K; most were tested at 423", 300°, 215", and 78°K. EXPERIMENTAL RESULTS Flow Stress vs Strain and Temperature. Typical true stress-true strain curves for thorium are shown in Fig. 1 for several temperatures over the range 473" to 78°K. The curves for 78", 215", 300") and 423°K were obtained from strain-rate change tests using the lower (0.005 min-') or base strain-rate values of stress. Additional tests, using the same base strain rate at different strain-rate ratios, gave curves which virtually superposed on those shown, indicating that strain-rate changes did not materially influence the work-hardening characteristics at the base strain rate. The curves for 273") 373") and 473°K were standard tensile tests at 0.005 min-'. The behavior of the flow stress with temperature is

Jan 1, 1968