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By W. S. Reid

In March, 1938, E. P. Fleming, metallurgist for the American Smelting and Refining Co. inaugurated an investigation into the possibilities of recirculating the gases from Dwight-Lloyd sintering machines operating on lead charge, with the twofold object of concentration of the SO2 content and reduction in volume of total gas produced. The possibility of recovering a commercial grade of SO2 gas from D & L machines operating on lead charge had previously been considered by several investigators. Early History of Recirculation The Selby Smelter Commission Report, published by the Bureau of Mines in 1914, contains a chapter by A. E. Wells regarding results obtained at Selby, wherein some of the richer gas was recirculated through a hood over the pallets. Oldright and Miller of the U. S. Bureau of Mines had also made tests at Trail, B.C., and at Kellogg, Idaho. R. C. Rutherford, while at the Chihuahua, Mexico, Smelter of the American Smelting and Refining Co., in May, 1937, proposed recirculation of D & L gases to decrease the volume of gas handled by the baghouse. At none of these plants, however, was the operation commercialized. In July, 1938, Mr. Fleming, in correspondence with the Selby Plant, inquired regarding the possibility of obtaining 6 pct SO2 gas from the Selby D & L machines. At that time, the writer advised that there was slight possibility of obtaining 6 pct SO2 gas without re- circulation, but believed that it was possible with recirculation, and that experimental work toward that end should be tried at some plant where spare D & L machines were available. The foregoing statement was based on the following information then available— 1. Tests on Selby first-over machines showed 2.28 pct SO2 from first windbox and 1.03 pct SO2 from second windbox, and corresponding figures for second-over charge of 0.81 pct SO2 for first windbox and 0.08 pct SO2 for second windbox. 2. Oldright and Miller (US. Bureau of Mines) in 1932 at Bunker Hill, on 42 in. X 22 ft machines found: a. First-over charge—Maximum SO2 concentration (leaving cake) of 9.5 pct. b. First-over charge—SO2 concentration of over 8 pct from the 4 ft to the 12 ft points beyond the front dead-plate and that the concentration then dropped rapidly. c. That approximately 80 pct of the total sulphur eliminated on the second-over machines occurred during the travel of the pallets from the 1 ft to the 6 ft distances from the dead-plate. d. That approximately 94 pct of the total sulphur eliminated on the second-over machines occurred over the first windox. 3. Oldright and Miller (US. Bureau of Mines) in 1932, at Trail, on 42 in. X 50 ft machines found: a. First-over charge—SO2 varied from 2.0 pct to 5.5 pct (leaving cake) from the 12 ft to 28 ft points from the deadplate. b. That the average SO2 increased from 1.0 pct at 7 ft from dead-plate to maximum of 3.3 pct at 20 ft, then dropped to 1.5 pct at 40 ft. c. That on a 22 ft, second-over machine with an 11 in. bed the SO2 varied from 4.5 pct to 6.5 pct from the 2 ft to the 8 ft points from the dead-plate. d. That on the final roast, the SO2 concentration also varied across the pallets; that is, 2 1/2 pct at the side, increasing to 6.0 pct, 5 in. in, and to 7.0 pct at 10 in. to 20 in. in, then decreased vice versa at the opposite side. e. Concluded that most of the sulphur on a 22 ft machine was removed over the first 7 ft of the first windbox; therefore, they partitioned the first windbox so that the exit gas from the second 4 ft section was returned to the surface of the pallets over the fist 7 ft section, and during a seven-day trial the gas from the 4 ft section averaged 2.4 pct SO2, while the recirculated gas from the first 7 ft section only increased to 3.8 pct SO2. (Excess suction over the 7 ft section to prevent escape of SO2 laden gas from the 4 ft section caused dilution by air.)

Jan 1, 1950

By J. F. Radavich

Many heats of steel of low carbon value have been known to produce brittle pieces of steel. The brittleness is believed to be due to the impurities located within the grain boundaries. Such brittle steels have been examined with an optical microscope to ascertain the nature and the amount of the impurities present at the grain boundaries. Due to the relatively low resolving power of the optical microscope, the impurities are not visible in fine detail. The writer obtained some sheet steel and proceeded to determine the location of the impurities and to show the application of the electron microscope to the study of grain boundaries. One sample was known to be capable of becoming embrittled, whereas another sample was believed to be much less susceptible to embrittlement. Treatment of Specimens The specimens were embrittled by annealing above the A3 point under mildly oxidizing conditions. One piece of ingot iron could not withstand a 90" bend, whereas another piece of ingot iron was not affected and could withstand a 90" bend. The brittle piece was then annealed at a high temperature in a hydrogen atmosphere. The annealed ingot iron was termed cured and could withstand a 90" bend very easily. The three specimens examined will be designated as brittle, good. and cured in the discussion that follows. Procedure The sizes of the specimens were as follows: one piece of brittle ingot iron-3/8 by 35 in.; one piece of good ingot iron-96 by 1/8 in.; one piece of cured ingot iron-36 by 54 in. The specimens were too small to be polished by hand and therefore were mounted in bakelite. The polishing procedure was carried out in the conventional manner with the use of 1/0 through 3/0 papers, and the final polish was done with alumina on a billiard cloth. The specimens were then etched in a 4 pct solution of picral in alcohol, and then they were examined through an optical microscope. An area was chosen that showed distinct grain boundaries, and an effort was made to keep near this area when pulling the replicas REPLICA TECHNIQIJE The replica technique used in the preparation of the replicas for examination under the electron microscope is described in Electron Metallography.' It consists essentially of the following steps: 1. Obtaining a suitably etched specimen. 2. Applying a swab of ethylene di-chloride on the surface. 3. Applying a formvar solution on the surface. 4. Placing a screen on any desired spot. 5. Breathing on the fornivar layer. 6. Applying scotch tape on the screen and film. 7. Pulling the film and the screen up with the Scotch tape. 8. Separating the screen from the Scotch tape. This replica technique is very similar to the one described by Harker and Shaefer. However, with the added step, the percentage of replicas removed is very much higher regardless of the length of the time from the etching of the specimen to the actual pulling of the replica. The replicas were then shadow cast with manganese at a filament height to replica distance ratio of 1 1/2:7. This produced a very high contrast replica for use in the electron microscope. One of the dificulties encountered with this study was the restricted area of the specimen. The width of the specimens was the same as that of the 200 mesh nickel supporting screen. In order to increase the effective area, the screens were cut down as shown in Fig 1. The arrow indicates the direction in which the replica was pulled. This operation made it possible to obtain a large percentage of good replicas. Fig 3 shows an electron micrograph of a brittle piece of ingot iron and a grain boundary that was polished mechanically. The surface is very rough probably due to the incomplete removal of the flowed layer by the picral etchant. The grain boundary does show evidence of impurities. It was decided to electropolish the specimens to obtain a much smoother surface than the one obtained by mechanical polishing. ELECTROPOLISHING The specimens were cut in half to expose the metal on the back side. The exposed metal had sufficient area to make good electrical contact and electropolishing was carried out easily. The conditions for electropolishing were 0.9 amp, 35 volts, and 25 sec. in an electrolyte composed of 850 cc of ethyl alcohol, 100 cc distilled water, and 50 cc of perchloric acid. The polished specimens were then etched in the 4 pct picral solution for a shorter time than was necessary for

Jan 1, 1950

By Shiou-Chuan Sun

THIS paper presents the design and operation of a frothmeter capable of measuring the frothing characteristics of pine oils and other frothing reagents. The experimental data show that the frothability of pine oil is governed by: 1-rate of aeration, 2-time of aeration, 3-height of liquid column, 4-chemical composition of pine oil, 5-pH value of solution, 6-temperature of, solution, and 7-concentration of pine oil in solution. The effect of mineral particles on the behavior of froth also was studied, and the results can be found in a separate paper.1 The results also show that the relative frothabilities of pine oils in the frothmeter generally correlate with those in actual flotation, provided that other factors are kept constant. In addition to pine oils, the other well-established flotation frothers were tested, and the results are included. In this paper, compressed air frothing is the frothing process performed by means of purified compressed air, whereas sucked air frothing is the frothing process accomplished by purified air sucked into the glass cylinder by a vacuum system. The term vacuum frothing denotes that froth was formed by degassing of the air-saturated liquid under a closed vacuum system. Apparatus The frothmeter, shown in Fig. 1, is capable of reproducibly measuring the volume and persistence of froth as well as the volume of air bubbles entrapped in the liquid and is capable of being used for compressed air frothing, sucked air frothing, and vacuum frothing. Fig. la shows that for compressed air frothing, the apparatus consists of an airflow regulating system, 1-3; a purifying and drying system, 4-8; a standardized flowmeter to measure the rate of airflow from zero to 500 cc per sec, 9; and a graduated glass cylinder, 13; equipped with an air regulating stopcock, 10; an air chamber, 11; and a fritted glass disk to produce froth, 12. The fritted glass disk, 5 cm in diam and 0.3 cm thick, has an average pore diameter of 85 to 145 microns. The pyrex glass cylinder has a uniform ID of 5.588 cm and an effective height of 63 cm. The inside cross-sectional area of the glass cylinder was calculated to be 24.53 sq cm, or 3.8 sq in. For sucked air frothing, Fig. lb shows that the apparatus for compressed air frothing is used again, with the following modifications: 1-compressed air and its regulating system, 1-3, are eliminated; and 2-a vacuum system, 16, equipped with a vapor trap, 15, and a vacuum manometer, 17, is added. The vacuum system can be .either a water aspirator or a laboratory vacuum pump. Any desired rate of airflow can be drawn into the glass cylinder, 13, by adjusting the opening of the air regulating stopcock, 10. The sucked air stream is cleaned by the purifing and drying system, 4-8, before entering the glass cylinder, 13. When this setup is used for vacuum frothing, the air regulating stopcock is closed. The frothmeter has been used for almost 3 years and has proved to give reproducible results, as illustrated in Table I. With a magnifying glass and suitable illumination, the frothmeter also can be used to study the attachment of air bubbles to coarse mineral particles.2 Experimental Procedures Except where otherwise stated, the data presented were established by means of the compressed air method. The volume and persistence of froth were recorded respectively at the end of 4 and 6 min of aeration at a constant rate of airflow of 29.3 cc per sec which is equivalent to 71.6 cc per sq cm per min, or 462.6 cc per sq in. per min. The aqueous solution for each test, containing 1000 cc of distilled water and 19.2 ± 0.5 mg frothing reagent, was adjusted to a pH of 6.9 ± 0.2. The volume of froth is expressed as cubic centimeter per square centimeter and is equivalent to the height of the froth column (the distance between the bottom and the meniscus of the froth). The volume of froth was obtained by multiplying the height of froth by the cross-sectional area of the glass cylinder, 24.53 sq cm. Before each test, the glass cylinder, 13, was cleaned thoroughly with jets of tap water, ethyl alcohol, tap water, cleaning solution, tap water, and finally distilled water. The cylinder with stopcock,

Jan 1, 1952

By W. R. Hudspeth

AS an outgrowth of its spodumene recovery operation at Kings Mountain, N. C., Foote Mineral Co. has been recovering a heavy mineral by-product. Foote leased this idle plant in 1951, reactivated it, using a new spodumene recovery process, and purchased plant and properties in October 1951. While the operation at Kings Mountain is primarily concerned with the production of spodumene concentrate, pilot plant work determined that the pegmatites also contained heavy minerals including cassiterite. Plans were made to recover the heavy minerals as a by-product and the flowsheet incorporated these facilities when the mill was modified for the new spodumene recovery process. The orebodies consist of spodumene, feldspar, quartz and mica. Apatite, tourmaline, and beryl are present in small quantities. The wall rock is pre- dominantly hornblende shist. The heavy minerals, including cassiterite, columbite, pyrrhotite, monazite, pyrite, and rutile represent about 0.2 pct of the ore. The fine-grained heavy minerals are disseminated throughout the dikes, apparently unassociated with the spodumene. The pegmatites are quarried and secondary breakage is by mud-capping and block-holing. Power shovels load into trucks transporting the ore to a coarse ore bin. A Telesmith 10x36-in. apron feeder delivers the ore to an 18x36 in. Traylor Jaw crusher adjusted to discharge -3 in. product to a primary conveyor. The conveyor delivers to a 4x5-ft Tyrock single deck vibrating screen using 3/4 in. cloth. The screen undersize is elevated to the crushed ore bin. Screen oversize goes to an Allis-Chalmers Hydrocone Crusher fitted with 4 in. concave and set to deliver approximately 66 pct minus 3/4 in. The crusher discharge returns to the primary conveyor. The crushing and screening installation has a capacity of about 60 tons per hour. Spirals The crushed ore is delivered at a rate of 350 tons per day to two 6x8-ft Hardinge Pebble Mills, equipped with 20 mesh Ton-Cap trommel screens. The screen oversize is pumped to a 12-in. hydroclone for primary desliming. The hydroclone underfl spirals. There is no heavy mineral loss in the hydro-clone overflow. The spirals bank consists of eight 5-turn Model 24-A Humphreys Spirals. The top port and the last four ports of each spiral are blanked, the remaining nine port splitters are adjusted to remove about 5 pct feed weight. The heavy mineral rougher concentrates are upgraded on a Deister Overstrom table. The spiral concentrates contain approximately 4 pct heavy mineral, and the spiral reject, which goes to another section of the plant for spodumene recovery, contains about 0.03 pct heavy mineral. There is an interesting feature in the spirals installation. An adjustable splitter mounted on the discharge boxes splits out a mica fines product containing very little heavy mineral. The mica product is cleaned by spiralling and screening. Thus the spirals recover two products; mica, and a heavy mineral rougher concentrate. Table Treatment The rougher spiral concentrate goes to a Deister Plato table, modified to receive a Deister-Overstrom No. 6 rubber cover with sand riffles. The table is operated with a 5/8 in. stroke, 270 strokes per minute, and a slope of 1/2 in. per ft from feed to tailings side. There is no slope adjustment from motion to concentrate end. Wash water consumption is relatively high, since the large spodumene grains tend to report with the fine heavy minerals. A middling band about 4 in. wide is maintained in order to produce clean concentrate. The middling, representing about 10 pct of table feed, is recirculated by air-lift. A band of concentrate grade coarse spodumene occurs just below the middling. This is removed and delivered to concentrate storage. The table tailing, containing approximately 0.7 pct heavy minerals, is returned to the spodumene feed preparation circuit. The heavy mineral table concentrates are approximately 45 pct cassiterite, 33 pct columbite, 14 pct pyrrhotite and 8 pct monazite, together, with some rutile, pyrite, and copper from blasting wire. Concentrate is collected at 24 hour intervals. and dried. If the concentrate remains in wet storage appreciably longer surface oxidation takes place which seriously interferes with the subsequent magnetic separation process. About 150 lb of heavy mineral concentrate is produced per 24 hours and shipped to the company's plant at Exton, Pa. for final separation into tin and columbium concentrates.

Jan 1, 1952

By D. J. McAdam

In a series of papers the author and associates have discussed the influence of temperature on the tensile properties of metals.11-18 These papers present much information about the influence of temperature and the stress system on the conventional indices of mechanical properties, with special attention to the fracture stress. A recent study of the data, however, has revealed much additional information about the influence of temperature on the fundamental factors involved in the flow of metals. The present paper presents results of this study. Attention will be confined almost entirely to results derived from tension tests of unnotched cylindrical specimens at strain rates a little slower than those used in ordinary tension tests. According to a concept first presented by Ludwik and elaborated in recent papers by others,8,9,22,23 the mechanical state of a metal depends on the total plastic strain, but not on the temperature during straining, provided that the only structural changes are those essential to plastic deformation. In the summer of 1948, however, the author made the previously mentioned study of results of a general investigation by the author and associates and reached the conclusion that the mechanical state depends not only on the total strain, but also on the temperature during the straining. A number of diagrams were then prepared. These conclusions were presented without diagrams in a discussion last October of a paper by Dorn, Goldberg and Tietz.2 The metals used in the investigation on which this paper is based were Monel and oxygen-free copper. The Monel was supplied by the International Nickel Co. through the courtesy of Dr. W. A. Mudge. The copper was supplied by the Scomet Engineering Co. through the courtesy of Dr. Sidney Rolle. The data to be presented are based on results of tests at temperatures ranging between 165 and — 188°C. Description of the apparatus and methods of test are given in previous papers.1011'1"2 The present paper is the first part of the general discussion of the influence to temperature on the stress-strain-energy relationship for metals. The next paper will deal with metals that are subject to structural changes other than those induced solely by plastic deformation. Influence of Temperature and Plastic Strain on the Flow Stress of Monel and Copper For a study of the influence of temperature on the stress-strain relationship, flow-stress curves obtained with annealed metals at various temperatures will be compared with curves obtained with the same metals after cold drawing or cold rolling at room temperature. Diagrams thus obtained with Monel and copper are shown in Fig 1 to 8. Fig 1 to 7 show the variation of the flow stress with temperature and plastic strain; Fig 8 is a diagram of a different type, derived from Fig 4 to 7. In Fig 1 to 7 strain is expressed in terms of A0/A, in which A0, and A represent the initial and current areas of cross-section. Since values of Ao/A are represented on a logarithmic scale, abscissas are proportional to true strains; moreover, the true strains representing prior plastic deformation and those representing subsequent strain during a tension test are directly additive. Fig 1 shows flow-stress curves obtained with annealed Monel. Five of the curves are based on results of tension tests. Between yield and the maximum load, the flow was under longitudinal tensile stress; between the maximum load and fracture, the local contraction induced transverse radial tensile stress. The portions of curves designated F, therefore, represent flow with increasing radial stress ratio, the ratio of the transverse stress S3 to the longitudinal stress Si. Curve Fo is based on the ultimate stresses of specimens taken from bars that had been cold drawn various amounts.17 Since the tensile stress at the maximum load is unidirectional, curve Fo represents the course that a flow-stress curve would take if the stress during an entire tension test could be kept unidirectional. The flow-stress curve F obtained at room temperature (Fig 1) has been established accurately by numerous measurements of the diameter of the specimen during the extension from yield to fracture.17 At the time of the experiments, however, no apparatus was available for measuring the diameter during tension tests at low temperatures. Nevertheless, curves have been established to represent with sufficient accuracy the flow at low temperatures. Each flow-stress curve must be tangent to a curve U, which starts at a point representing the ultimate stress of annealed metal. Since the ultimate stress is based on the area of

Jan 1, 1950

R. V. NorHis, Wilkes-Barre, Pa. (communication to the Secretary*) : The electric-haulage plant of the Short Mountain Colliery of the Lykens Valley Coal Co., mentioned by Messrs. Stoek and Harris as the earliest underground electric plant in the United States (and, I believe, the second in the world), was started July 23, 1887. The plant, designed by W. M. Schlessinger, consists of two motor-cars, each weighing about 5 tons and equipped with a 32-h.p. Union Electric Go. motor. The original general construction of the motor-cars is shown by Mr. Stoek; but they were rebuilt, the same year, with some important improvements in design; and, except for strengthening the frames and replacing the original pig-iron weights by a casting, they have not been greatly changed since that time. The generating-plant consists of two Union Electric Co. dynamos of 65-h.p. each, driven by an old 18- by 48-in. plain slide-valve engine; the ordinary voltage is 450 and the amperage varies from 40 to 200; the average indicated h.p. of the engine is about 75, with a steam-consumption of about 75 lb. per i.h.p. per hour; and as the cost of steam at this colliery is 8.11 cents per 1,000 lb.,the steam-cost per day is about $4.56.

Jan 1, 1904

By P. E. Phillips

INTRODUCTION Rocky Mountain Energy is the mining subsidiary of the Union Pacific Corporation, and has been active m uranium exploration since 1966. Since 1970, RME's uranium activities have been funded 50% by Mono Power, the fuels supply division of Southern California Edision. RME and Mono recognized the need for development of new methods for recovering low grade uranium deposits, and contacted Halliburton Services in regard to in situ leaching, because of Halliburton oil industry experience. As a result, a joint venture between the three parties was formed in 1974. BEAR CREEK The first ISL test was at the Bear Creek deposit in the Powder River Basin of Wyoming, about 60 miles north of Douglas. The mineralized sand is the tertiary Wasatch formation, which is an arkosic sandstone. The sand typically contains about 10% clay. The predominant clay being montmorillonite with some kaolin and illite. The roll front type trends occur along the flanks of old stream channels. This deposit was being considered for exploitation as an open pit mine. Routine amenability testing indicated it was quite amenable to a conventional acid leach, consuming about 50 lbs. of sulfuric acid per ton of ore in an agitation leach, while recovering more than 95% of the uranium. Hydrology testing indicated a permeability of about 1 darcy. The groundwater has a pH of about 8. 0 and TDS of about 1200. Test Facility The Bear Creek test was a summer-only operation, with no effort towards weather-proofing. Uranium was removed from the recovered leach solution by fixed bed ion-exchange columns. Loaded resin was eluted with strong sulfuric acid. The recovery plant was designed for simplicity of operation, with little concern for the grade or form of the yellowcake product. The plant was constructed of PVC piping and valves, fiberglass reinforced tanks, and stainless steel pumps. All waste streams were directed toward a lined evaporation pond. Wellfield The test pattern was a 30 foot radius 5 spot, with wells fully penetrating the 30 foot ore sand to a total depth of about 165 feet. The injection wells were three-inch PVC with slotted casing, while the producer was eight-inch I. D. , with a stainless steel screen. The eight-inch well was necessary in order to accommodate a six-inch stainless steel pump. Wells were cemented using cement baskets, at the top of the sand, to contain a latex acid resistant cement. Leach Conditions The lixiviant generally contained from five to seven gpl sulfuric acid, and about 0. 5 gpl hydrogen peroxide. The pH was generally 1.4 and EMF was usually -550 millivolts. Injection rates were rather variable from well to well, with a total injection rate between 12 and 25 GPM. Production rate was set at 25 GPM, since the production pump could not be throttled more than that. Approximately two pore volumes of solution were injected during the three-month test. Leach Results Injectivity was quite variable, but was generally rather poor, because of poor completion techniques. The problem stemmed from injecting before the injection wells had been completely cleaned of drilling mud. Pregnant solutions averaged about 50 ppm U308, with groundwater dilution varying from 10 to 50%, depending on the injection rate. Injectivity did decline with time, probably as a result of contamination of the well faces. A total of 1000 lbs U308 had been recovered when the test was shut down. This probably represented about 10% of the mineral under leach.

Jan 1, 1979

The Government has for disposal a large stock of horse-drawn vehicles that were produced during the war to transport and handle all kinds of army supplies. These vehicles consist of escort wagons, also the axles and wheels; ambulances, model 1909; sprinkler, wagons, buckboards, combat wagons, hand carts, water carts, ration carts, and medical carts. These vehicles are adapted to numerous commercial purposes. All were produced under the strictest Government rules, specifications, and supervision and are first class in every way.

Jan 6, 1919

By R. M. Jorda

The mechanism of parafin deposition and prevention has been studied in the laboratory using an apparatus which provides a quantitative means of studying parafin deposition on metal and plastic surfaces. The amount, hardness, adhesion, per cent wax and mean molecular weight of parafin deposits appear to be governed by surface roughness alone, all other conditions being constant. Tests of various plastic coatings indicate that most smooth, nonparafinic plastics are capable of reducing parafin deposits in oil wells, but flexible, highly polar, nonparafinic plastics are more suitable for providing long term resistance to parafin deposition in oil wells if the flow stream contains abrasive materials. INTRODUCTION The problem of paraffin deposition is one of long standing in the oil industry.' Crude oils often contain paraffins which precipitate and adhere to the liner, tubing, sucker rods and surface equipment as the temperature of the producing stream decreases in the normal course of flowing, gas lifting or pumping. Heavy paraffin deposits are undesirable because they reduce the effective size of the flow conduits and restrict the production rate from the well. Where severe paraffin deposition occurs, removal of the deposits by mechanical, thermal or other means is required, resulting in costly down time and increased operating costs. The troublesome paraffins are normal hydrocarbons ranging from approximately C15H38 to C38H78 mixed with small amounts of branched paraffins, monocyclic paraffins, polycyclic paraffins and aromatics.' The amount of paraffins found in crude oils varies from less than 1 to more than 30 per cent. Many publications are available which deal with this problem, and perhaps the most significant findings in recent literature are contained in a publication by Hunt3 ho developed the "cold spot tester", a really useful means of investigating paraffin deposition. Hunt's observations led to many generalized conclusions concerning the effect of surface roughness on paraffin deposits. He ascertained that there was an observable qualitative correlation between the severity of paraffin deposition and the roughness of the surfaces which he tested (cold rolled steel, stainless steel and several plastics). Because of the number of meaningful observations made by Hunt, his cold spot tester was modified somewhat and extensive tests were per- formed to study the quantitative relationship between surface roughness and the physical and chemical nature of paraffin deposits. LABORATORY TEST PROCEDURES The cold spot test apparatus consists of a flat circular plate mounted on a curved tube and positioned in a vessel containing a wax-oil solution (Fig. 1). The apparatus is arranged so that the temperature of the central portion of the circular plate can be varied by means of a circulating liquid stream; the test equipment includes provisions for maintaining a constant wax-oil solution temperature and stirring speed. In the paraffin deposition studies, the modified cold spot tester was used as follows. The cold spot probe consisted of a flat circular plat 2 in. in diameter and 1/8-in. thick positioned in the wax-oil solution kept at constant temperature. As in Hunt's earlier experiments," a cold liquid was circulated through a tube connected to the circular plate so that the liquid impinged on one side of the plate cooling the plate from the center outward, causing paraffin to deposit on the side of the plate exposed to the wax-oil solution.

Jan 1, 1967

By Jim D. Mote, Eugenia M. Howard, Willis L. Barmore, John E. Dorn

The effect of stress and temperature on the creep rate of Ag-33 at. pct A1 and Ag-33 at. pct Al-1 at. pct Zn for prismatic slip was determined over a range of temperatures from 440º to 700°K. The alloys exhibited a brief initial inverted transient creep over which the creep rate increased slightly to a steady-state value which depended only on the stress and temperature, regardless of the previous strain history. The steady-state creep rates were found to be given by: where the activation energy is independent of the stress and strain and agrees fairly well with that estimated for diffusion. The observed creep behavior was shown to be in qualitative agreement with a model based on the stress-induced local disordering in the vicinity of a dislocation. OVER the past fifteen years, considerable progress has been made in correlating the experimen-entally observed plastic behavior of pure metals over each temperature range with one or more of a series of theoretical strain-rate controlling dislocation mechanisms. Despite the current interest in the plastic behavior of intermediate phases and inter metallic compounds, however, very little has been done in identifying the operative dislocation mechanisms in these materials. It is anticipated that the plastic behavior of intermediate phases can be rationalized in terms of the same dislocation mechanisms that are appropriate to pure metals and a solid solutions, provided the additional complexities arising from crystal structure, bonding, long-range order, short-range order, and defect lattices are taken into account. As part of a more extensive investigation on the plastic behavior of intermediate phases, Mote, Tanaka, and Dorn1 recently reported on the effect of temperature on the yield strength for prismatic slip in the hexagonal Ag-33 at. pct A1 intermediate phase as recorded in Fig. 1: Over Region I the deformation was observed to take place as a result of the thermally-activated Peierls mechanism, and over Region II the athermal disordering mechanism applied. The experimental data at that time, however, were not sufficiently extensive to identify the thermally activated mechanisms operative over Region III. It is the purpose of this investigation to attempt to identify the mechanisms that are operative over this high-temperature region. It will be shown that the same mechanism operates all over Region Ill, although the activation energy for this mechanism is in good agreement with that for diffusion, the process cannot be attributed either to the motion of jogged screw dislocations or the climb of edge dislocations. The results, however, are in good qualitative agreement with stress-induced disordering localized at dislocations. EXPERIMENTAL PROCEDURE The alloys studied in this investigation were prepared from silver, aluminum, and zinc (each of purity greater than 99.995 pet) by induction melting under an argon atmosphere and chill casting in a copper mold. Rectangular bar single crystal specimens (1/4 by 1/8 in. in cross-sect ion) of Ag-33 at. pct Al were grown in vacuum by a modified Bridgman technique. Similar Ag-33 at. pct Zn specimens were produced by an identical technique employing an argon atmosphere. The specimens were so oriented that the angle 90-Xo between the tensile axis and the normal to the prismatic plane and the angle A, between the tensile axis and the slip direction were 45 ± 1 deg. The effect of a change in temperature on the creep rate and a change in stress on the creep rate were determined over the temperature range

Jan 1, 1963

By B. H. Caudle, A. R. Khan

The oil production performance of thin-oil-column type reservoirs producing entirely by natural water drive are discussed in this paper. The dimensionless production histories were obtained in a series of scaled porous-medium laboratory-model tests under varying effects of rate of production, mobility ratio across moving boundary, ratio of oil- and water-sand thickness and mobility ratio across fixed boundary including the effects of different residual oil saturations in the water-invaded regions. This scaled-model study of thin oil columns indicated that greater recovery of oil results for lower values of the following: rate of production, mobility ratio across the moving boundary, water-sand thickness relative to the oil-sand thickness, and mobility ratio across the fixed boundary or residual oil saturation in the water-invaded region of oil sand The results of the study are given as dimensionless production history plots which may be used to predict the performance of the field they represent. INTRODUCTION Oil fields producing under natural water drive can be classified into two major groups: (1) an "edge-water drive" reservoir group in which the water is encroaching from the reservoir periphery, and (2) the group of reservoirs in which the oil-sand is entirely underlain by an aquifer. Reservoirs in the second group are further subclassified as "bottom-water drive" reservoirs and "thin-oil-column" reservoirs. The latter reservoirs are characterized by their relatively equal oil- and water-sand thicknesses and by having both the oil and water zone relatively thin. When oil is produced from a water-drive reservoir by a partially penetrating well, water breaks through sooner or later before all of the displace-able oil is recovered. Many analyses of this general situation have been made with varying degrees of realism in their approaches, both theoretical and experimental5.6 in nature. Pertaining to the scaled laboratory model studies of natural water drives using porous media, detailed investigations have been made by Henley, et al.7 on bottom-water drive and by Caudle8 on edge-water drive reservoirs. No laboratory model studies, however, have been made to investigate the performance characteristics of thin-oil-column reservoirs. This paper presents the results of a study on scaled models of thin-oil-column reservoirs, operated under varying conditions corresponding to the actual field practices. SCALING PARAMETERS The object of scaling is to produce a one-to-one relationship between physical and dynamic parameters of the model -and prototype. The most comprehensive treatment of scaling techniques for oil reservoirs is given by Geertsma, et a1.,9 which covers two methods for arriving at dimensionless groups for scaling. Table 1 lists the scaling parameters suitable for creating kinematic and dynamic similarities between the model and the prototype in the variables considered for the thin-oil-column reservoirs. In order to achieve similarity it is essential that the dimensionless groups listed in Table 1 have equal values in the model and the protorype simulated. Since it has been established that the role of interfacial forces is neglible in gross fluid movement in a reservoir no attempt was made to scale capillary forces- Although there are reports describing Scaling criteria for these forces,10,ll consideration of the necessary but restrictive conditions for

Jan 1, 1970

By Verne E. Hooker, Robert M. Becker

The evaluation of in-situ rock stresses from measurements of the change in diameter of a borehole that is stress-relieved by overcoring has become a common practice. Generally the stress evaluation has been based on isotropic relations whereas rock in varying degrees is aniso tropic. A plane elasticity solution fora circular hole along one axis of an orthotropic medium has been adapted to evaluation of in situ stress. The necessary elastic parameters for this evaluation may conveniently be obtained from static tests on the overcore in conjunction with a consistent orthotropic thick-wall cylinder solution. The method and equations for the laboratory and field evaluations are summarized and illustrated. The determination of in-situ rock stresses from boreholc deformation measurements has gained widespread acceptance. Hastl measured the change in diameter of a borehole that was stress-relieved by drilling a larger concentric core; this overcoring method has produced a major portion of the field data for recent stress evaluations in rock. These evaluations are based on the elastic properties of the rock, which are conveniently determined by testing the overcore.6-8 The stress evaluation and the overcore testing procedures generally assume isotropic relations whereas rock is anisotropic in varying degrees. Recently, an anisotropic plane stress solution was adapted for evaluation of in-situ stress9 and a related plane strain solution was developed for the testing of stress-relief core. 10 The present paper unifies the stress evaluation and overcore testing procedures for a general class of anisotropic rock. Equations are presented for calculating the state of stress in a plane normal to the borehole, and a consistent thick-wall cylinder solution is given for determining the necessary elastic properties. In addition, a complete example of stress evaluation from laboratory and field data is presented, and the order of error in computing the state of stress from isotropic relations is illustrated. Several limitations of the results should be emphasized. All results assume small linearly elastic deformations of a homogeneous medium. Rock characterized by orthotropic, transversely isotropic, and isotropic elasticity is considered; however, the anisotropic results assume a special relation among certain elastic constants in addition to geometric orientation with respect to a plane of elastic symmetry. For some stress determinations in rock, these may be severe limitations. On the other hand, the anisotropic evaluation procedure involves little additional effort and is much more flexible than the corresponding isotropic evaluation procedure. The collection of field data is identical. The laboratory determination of elastic parameters is no more difficult and time-consuming for the anisotropic than for the isotropic model. Only the calculations require some additional effort for the anisotropic evaluation, and this additional effort is eliminated by use of a small computer. The flexibility of the anisotropic procedure is greater because more than two independent elastic constants are available in fitting rock data. For the special relationship assumed among orthotropic constants, five independent elastic constants are available for the determination of in-situ secondary principal stresses as compared with two independent elastic constants for the isotropic model. Much of the material presented is either directly from the literature or adapted from the literature through superposition or the usual transformations. Consequently, only enough detail for clarity of presentation is included. RELATIONS FROM ANISOTROPIC ELASTICITY Materials that have three mutually orthogonal planes of elastic symmetry are called orthotropic. By directing the axes of the coordinates perpendicular to these planes, Hooke's law for an orthotropic solid 11 is

Jan 1, 1970

By R. Schuhmann, G. W. Powell

The concept of local equilibrium is examined and, in particular, the applicability of the concept to two-phase binary diffusion couples is discussed. It is concluded that, if binary solid solutions are treated thermodynamically as ternary solutions, vacancies being the third component, then recent experimental observations of nonequilibrium interface compositions (i.e., compositions different from the phase diagram values) are consistent with a state of complete dynamic equilibrium at the interface. CLASSICAL approaches to diffusion and to other irreversible processes often utilize a postulate of "local equilibrium". That is, one assumes even in the presence of gradients, fluxes, and time changes of properties, a) that the Second Law can be formulated locally, and b) that thermodynamic equations of state among intensive properties are identical with those for equilibrium phases. A direct consequence of this assumption, for example, is that one would calculate the total entropy of a nonequilibrium phase simply by integrating the entropy density (eu per unit volume) over the volume of the phase, assuming that entropy density is the same function of energy and particle density as for equilibrium phases. In the study of diffusion and of diffusion-controlled phase transformations, metallurgists take this concept of local equilibrium for granted and utilize it automatically. In fact, experimental evidence of all kinds is overwhelming that "local equilibrium" is a valid limiting law, approached more and more closely as gradients and rates of change approach zero. On the other hand, we have neither experimental nor statistical thermodynamic proof that this principle of "local equilibrium" should remain rigorously valid at high gradients and for rapid processes. Theoretically, in fact, one would expect deviations because interactions between adjacent volume increments of material affect the evaluation of entropy. Also one observes experimentally structural and small energetic differences between equilibrium and nonequilibrium phases. The purpose of this paper is to present a thermodynamic framework for the study and correlation of deviations from strict local equilibrium in isothermal diffusion and related processes. This procedure, in effect, preserves the principle of local equilibrium by thermodynamically assigning the deviations from static equilibrium properties to a defect component. Although this theory is entirely phenomenological, the possibility does exist of correlating the theory with experimental observations of defects under favorable circumstances. The most immediate application appears to be to the equilibria at the interfaces in two-phase binary diffusion couples. A recent pertinent work by Eifert et al.1 has shown that the concentrations of aluminum in the a(fcc) and B(bcc) phases at the 0-8 interface in Cu:Cu-12.5 wt pct A1 diffusion couples are greater than those given by the phase diagram. It is postulated by these authors that the supersaturation of the o phase at the interface provides the driving force for the a-to-B lattice transformation; the excess free energy of the a phase, ?Gaxs, arising from the greater-than-equilibrium aluminum concentration is about 3 cal per g-atom. On the basis of the schematic free energy-composition diagram shown in Fig. 1, Eifert et al. concluded that the thermodynamic situation at the interface is one of the partial equilibrium; that is, = for the more mobile aluminum whereas will be reexamined in the latter part of this paper. THERMODYNAMIC PROPERTIES OF DEFECTS A rigorous analysis of the thermodynamics of defects requires an added degree of freedom in the Phase Rule sense, because the standard formulations of solution thermodynamics (partial molal properties of components, free energy minimization, equality of chemical potentials, and so forth) involve the implicit

Jan 1, 1970

By T. L. Berger, M. C. lnman, M. F. Rose

AFTER shock loading, mechanical twinning has been observed by several authors1-4 for a variety of fcc metals and alloys. It has been shown2,3 that low stacking fault energy materials deform primarily by the formation of mechanical twins and stacking faults during dynamic loading. Further, Inman, Murr, and Rose2 have shown that a correlation exists between the average hardness and the volume percent of mechanically twinned material in stainless steel. It has been observed in nickel' that mechanical twins are produced during shock deformation if the peak pressure associated with the shock wave is greater than 350kbar. It is the purpose of this work to discuss shock-hardening mechanisms in nickel and to determine to what extent the initial condition influences the final response. The "flying plate technique" was used to generate planar shock waves with peak pressures as high as 710 kbar. The details of the technique5" have been discussed elsewhere and will not be repeated here. The material used in this study was polycrystalline nickel of 99.98 pct purity and had an initial grain size of 0.18 mm. Prior to any deformation, all samples were given a stress-relief anneal of 6 hr at 600°C in a vacuum furnace. After annealing, the initial condition of the samples was changed by cold rolling individual samples from 0 pct to a maximum of 80 pct reduction in thickness. This provided samples with controlled initial histories for shock deformation. Immediately after shock loading, the specimens were slowed and quenched by suitable arrangement of buffer material and water bath. This technique minimized specimen damage and the effects of shock heating on the samples. Since deformation twins in high stacking fault energy fcc metals are only produced at high stress levels, the initial defect configuration prior to mechanical twinning should greatly influence the number of twins formed. In fact, Zukas and Fowler7 have found that prestraining in iron and steel greatly suppresses the formation of mechanical twins during the shock deformation process. Following the methods of Warren and warekois8 and Cohen and Wagner,9 X-ray diffraction profile analysis was performed to determine the incidence of stacking faults and mechanical twins in the deformed nickel. Analysis was made on samples in the annealed, cold-rolled, shock-loaded, and cold-rolled—shock-loaded states. The estimated accuracy of the peak position measurements is *0.01 deg in 2?. Therefore the accuracy in the measurement of the relative peak shifts between the (400) and (222) diffraction line profiles is on the order of *0.04 deg in 2?. None of our measurements indicated peak shifts greater than 0.04 in 28. This would correspond to a fault density of -1 pct and sets the limit on the sensitivity of our instrument. Similarly, analysis of the shift in the center of gravity of the diffraction line profiles yields the minimum measurable value of the twin fault probabilitya to be -0.002. Fig. 1 shows mechanical twinning in nickel shock-loaded to 400 kbar. In this photograph, fault intersections are clearly visible. The thickness of the individual fault lamellae was determined from the image widths of their lines of intersections by the

Jan 1, 1968

By L. Yarborough, L. R. Smith

This paper presents results of a laboratory study of retrograde condensate recovery by revaporization into dry injection gas. Flow tests were performed in 10.6-ft long sand packs at 100F and 1,500 psi. In three runs methane revaporized the liquid from a n-pentane-methane mixture in the presence of immobile water. TWO of these tests were water-wet, and the third was totally oil-wet. In the three runs n-pentane recovery was complete after 2.5 hydrocarbon PV of injection. There was no significant performance difference between the two wettability extremes. In a fourth experiment, a methane-hydrogen sulfide mixture revaporized a synthetic light, sour condensate. No water saturation was present. Equilibrium compositions and volumetric data were obtained for the four-component condensate. The heavy component, n-beptane, was removed after 6 PV production. Comparison of the effluent fluid compositions with known equilibrium data shows that the flowing fluid was equilibrium vapor and that the mixing zone between equilibrium vapor and dry injection gas was short. Data indicated that complete recovery of retrograde liquid occurred after it was contacted by a sufficient quantity of dry gas. INTRODUCTION When pressure declines below the fluid dew point in a gas condensate reservoir, a liquid phase forms. In this process, referred to as retrograde condensation, the quantity of liquid formed is frequently small enough that the liquid is not a flowing phase. To prevent loss of valuable retrograde liquids, the process of dry gas cycling has been employed for several years as a more or less standard practice. In this procedure the reservoir pressure is maintained above the fluid dew point so that the liquid components may be produced as vapor and then separated at the surface. Although full pressure maintenance by gas cycling seems ideal in terms of preventing liquids loss, several factors can reduce the atuactiveness of such an operation. From a study of a condensate reservoir in Alberta, Canada, Havlena et a1.1 con-cluded that cycling under conditions of declining pressure leads to economic advantages and to a high recovery of hydrocarbon liquids. This study considered effects of volumetric sweep efficiency, retrograde behavior of the original wet gas and revaporization characteristics of the retrograde liquid when contacted by dry gas. The first major work concerning revaporization of liquid in a gas condensate system is that of Standing et a1.2 Calculations based upon the PVT behavior of a recombined gas condensate fluid indicated that all retrograde liquid can be recovered if it is contacted by a sufficient quantity of dry gas. The paper considered the effect of variable permeability upon the recovery of retrograde liquid. Standing et al. concluded that recovery of heavier components in the retrograde liquid is greatest if reservoir pressure is allowed to decline below the dew point prior to dry gas injection. Since the work of Standing et al., several laboratory studies have been reported which show that recovery of hydrocarbon liquids by vaporization into dry injected gas can contribute to increased recovery above that obtained by ordinary production practices. Vaporization from retrograde condensate,3 conventional oil4-7 and volatile oil8 reservoirs has been considered. There is little work that deals with revaporization recovery from condensate reservoirs. This study demonstrates that vapor-liquid equilibrium exists when a dry gas is injected into a porous medium containing retrograde condensate; investigates the effect of wettability on revaporization of retrograde condensate; and provides an indication of the amount of dry gas necessary to

Jan 1, 1969

By R. I. Jaffee, F. C. Holden, H. R. Ogden

Ti-Mn alloys were studied in order to determine the factors affecting the mechanical properties of &stabilized titanium alloys. The principal compositional factors have been found to be solid-solution strengthening, the martensitic transformation, and instability of the P phase. Structural factors, such as grain size and shape, were found to have more influence on ductility and toughness than on strength. THE alloys of titanium with the &stabilizing elements offer the chief hope for developing useful heat treatments. Conversely, the heat-treatment response possible with the p-stabilizing elements causes difficulties such as weld embrittlement and thermal instability during service at elevated temperature. Therefore, it is of considerable technical importance to understand the factors that govern the heat-treatment responses in these alloys, so as to be able to soften the alloys if they are embrittled by an adventitious heat treatment, to render them stable in service, or to harden them while maintaining adequate ductility and toughness. The Ti-Mn system is a good example with which to demonstrate the factors that govern strength and heat-treatment response in. a P-stabilized system. The region of the a-j3 transformation, after the work of Maykuth, Ogden, and Jaffee,' is shown in Fig. 1. The a solubilities are low. This means that, in the two-phase a-p field, partition of manganese between the two phases occurs practically only to the P phase. The solid-solution effects are therefore chiefly the result of solution in the ,8 phase. The eutectoid occurs at 20 pct Mn and 550°C, and proceeds very sluggishly. It can be ignored in heat treatments in hypo-eutectoid alloys, except for long-time storage at low temperatures below the eutectoid temperature. Even here, there is some question that diffusion proceeds far enough to involve eutectoid decomposition. Three compositional factors bear on the mechanical properties and structure of titanium a-P alloys. These are: 1—solid-solution strengthening, 2—mar-tensite transformation, and 3—P instability. Combined with the purely structural factors of grain size and shape, these govern the properties of the alloys. Perhaps the most important factor is solid-solution strengthening. The facts that manganese dissolves in a titanium to a maximum of only 0.5 pct and most of the manganese partitions to the p phase dominate the structure and properties of the a-/3 alloys. Because of the overwhelming preference of manganese for the ,3 phase, the P phase is harder and the a phase is softer. The relative amounts of both phases may be modified by heat treatment in the a-P field as application of the lever rule in the two-phase field clearly shows. A critical temperature in the Ti-Mn diagram is 800°C. This is the P transus temperature of the 6.4 pct Mn alloy, which has the lowest manganese content which will form all retained-P phase on quenching to room temperature. Any quench performed from below 800°C will produce a structure consisting of only a, a plus retained P, or retained p, for alloys of the compositions used in this work. For alloys containing less than 6.4 pct Mn, any quench from above 800°C will always result in structures

Jan 1, 1955

By B. K. Larkin, H. R. Bailey

One of the most complicated and potentially one of the most promising secondary recovery methods is that of underground combustion. A number of field tests1,2,3 have been performed recently, apparently indicating that the underground combustion process is technically feasible. Relatively little has been published concerning laboratory or theoretical investigations of the underground combustion process. A few results of laboratory tube runs have been published4,5 and these data are valuable in understanding the process. The tube run data also emphasize the complexity of the thermal recovery process. Under various conditions, problems in heat transfer, multiphase fluid flow and combustion rates arise. For example, at low temperatures the combustion process proceeds so slowly that the front cannot be propagated. It is a problem in heat transfer to predict what injection rate of air is necessary to sustain combustion in a particular reservoir. Certain fluid flow aspects of underground combustion have been studied by Wilson, et a13. In the development of some of the flow equations, assumptions of adiabatic combustion were made. Vogel and Krueger1 have devised an analog model of the heat conduction process for a constant temperature cylindrical source moving radially outward in a homogeneous conducting medium. Jenkins and Ramey7, in a discussion of the Vogel and Krueger paper, present an analytical solution of a heat conduction problem related to problems considered by Vogel and Krueger. In the present paper an idealized model of the heat conduction problem is considered, which is more general than the model of Vogel and Krueger or Jenkins and Ramey. In particular, initial well heating, vertical heat losses and arbitrary frontal velocities are included. Equations for the temperature are obtained in terms of integrals. These integrals have been evaluated numerically for the case of frontal movement corresponding to a constant air injection rate and the case of constant frontal velocity. These results are presented graphically. From these graphs one may estimate conditions under which nearly adiabatic temperatures are obtained. The application of these results requires some knowledge of reservoir thermal properties, combustion rates and residual fuel content. Assuming no vertical losses it is possible to obtain explicit evaluations of these integrals in the linear con- stant velocity case and in the radial case corresponding to a constant air injection rate. PRESENTATION OF RESULTS The geometry of the radial system is illustrated in Fig. 1 where the reservoir is represented as a slab of thickness h. By making an energy balance for an infinitesimal volume, one obtains the following equation. T= x T+F(z.r).........(1) where F (z,r) =HWv1/pc (r-r1), if z h/2 = 0, if z >h/2 . In Eq. 1, V- represents the Laplacian operator and 8 is the Dirac delta function. Eq. 1 is the well-known diff-sion equation with a source term and may be applied to a linear system. For example, if the source is moving in the direction of the x axis, then the argument of the delta function is x - 1,. In deriving Eq. 1 the following approximations were made concerning the actual combustion process: (1) all heat transfer is by conduction in a homogeneous medium, (2) the formations bounding the reservoir have the same thermal properties as the reservoir, (3) the combustion fuel is consumed instantaneously as the front arrives, (4) there is a constant fuel concentration

By R. F. Domagala, D. J. McPherson

Iodide zirconium was combined with calculated amounts of ZrO2 or master alloys and arc-melted. Annealing treatments were carried out at 21 temperature levels. Metallographic examination of the heat treated specimens permitted construction of the binary phase diagram from zirconium to ZrO2. Oxygen additions to zirconium raise the transformation temperature as well as the melting point. Features of the diagram include the peritectic formation of beta, the formation of alpha directly from the melt, an intermediate phase ZrOB with a' range of homogeneity, and a eutectic between alpha and Zr02. PHASE relationships in the Zr-0 system were determined in the range 0 to 66. 7 atomic pct 0 (ZrO,). Arc-melted alloys were annealed at temperature levels between 600" and 2000°C. Determination of the phase boundaries was accomplished by metallographic evaluation of specimens quenched from the various temperatures. Incipient melting techniques were used to determine solidus curves, and X-ray diffraction work was employed to study the lattice parameters of the a solid solution and the phase ZrO,. Experimental Procedures Westinghouse "Grade 1" iodide zirconium crystal bar (approximately 99.8 pct pure) was employed for the investigation. This material is substantially free of the impurity inclusions characteristic of most zirconium metal. Previous work has shown it to be the most satisfactory grade for phase diagram studies. The zirconium crystal bar, as-received, was coated with corrosion product from autoclave tests by which its grade designation is determined. The bars were sand blasted lightly, pickled for 1 min in a 20 pct HN0,-5 pct HF aqueous solution, rinsed in water and acetone, and dried. The bars were rolled to about 1/32 in. strip, cut into 10 in. lengths, and pickled again. The material was sheared to approximately Y4 in. squares, cleaned with acetone, and stored for use. Two pounds of specially prepared "chemically pure," and 100 grams of spectrographic grade ZrO, were obtained for the preparation of alloys. The "Specpure" ZrO, was obtained from Johnson, Mat-they Co.. Ltd.. and Titanium Alloy Manufacturing Div. of National Lead Co. supplied the other grade of oxide. The "chemically pure" material (henceforth referred to as C.P. ZrO,) was used for the preparation of all alloys employed in the determination of phase relationships. A limited number of alloys were prepared with the "Specpure" oxide to recheck certain phase boundaries. Analyses of the two grades of oxide are given in Table I. The C.P. ZrOI was received in powder form, not suitable for arc melting. Therefore, this material was compressed to wafers 1 in. in diameter and about Vn in. thick. These were segmented and stored for use. The "Specpure" material, in the form of small granules, was suitable for use in the as-received condition. A nonconsumable electrode arc-melting furnace was used to prepare alloys. A water-cooled copper crucible and tungsten-tipped electrode were employed. The material was placed in the crucible and rapidly melted under a protective atmosphere of helium gas by striking the arc on a tungsten stud and directing it upon the charge material. Details of operation, including drawings of this type furnace, have been published.'

Jan 1, 1955

By R. T. Hukki

This paper presents a preliminary analysis of the fundamental relationship between the net energy used and the respective product size throughout the entire range of sizes covered by crushing and grinding, and an attempt to find a sensible correlation between the existing theories. Walker, Lewis, McAdams, and Gilliland' have given the following differential equation of a general form for comminution: dE = -C§ [1] where E is the net energy required per unit weight in a certain process of comminution; x is the factor indicating the fineness of the product; n is the exponent indicating the order of the process, and C is a constant related with the material, units chosen, etc. H exponent n in the above equation is replaced by numerical figures 2, 1, and 1 1/2, the integrated form of the general equation leads to the well known fundamental theories represented by the law of von Rittinger,' law of Kick, and the third theory of comminution by Bond, respectively. The total net energies (E) from infinite feed size to a product of size x are as follows: The net energy required in a certain process of comminution is proportional to the new surface developed according to the law of von Rittinger, to the weight or size of the bodies treated according to the law of Kick, and to the length of the new cracks formed which initiate breakage according to the theory and explanation by Bond. On a logarithmic paper, where particle size is presented on the abscissa and energy consumption on the ordinate (see Fig. 21, all three relationships are represented by straight lines. The slope m of the line according to the law of von Rittinger is equal to -1.0; of Kick, 0; and of Bond, -0.5. Experimental evidence in favor of the law of Rittinger has been presented, e.g., by Gross and zimmerley5 on quartz crushed in a drop weight crusher and evaluated for surface by the method of dissolution, by Dean on magnetite crushed by a similar method and evaluated for surface by the determination of coersive force, by piret7 and co-workers on a group of minerals crushed again by a similar method as well as by compression and evaluated for surface by permeability and gas adsorption methods, and by schellinger8 on a group of minerals ground in a calorimetric ball mill and evaluated for surface by gas adsorption. Experimental evidence in favor of the law of Kick seems to be scant in the field of comminution. On the other hand, in the field of mechanical engineering Kick's law seems to be of fundamental nature in processes such as cutting, pressing, shaping, and rolling of metallic substances. Experimental evidence in favor of the third theory has been provided by Bond." To a large extent, data are based on the vast amount of grindability tests performed in the laboratories of Allis-Chalmers Manufacturing Co. In addition to the devoted proponents of one or the other of the basic theories listed above, certain investigators have indicated that one of the theories might be applied for a certain range of sizes, while another theory might be used for other sizes. In a discussion of a paper by Bond," Dobie" presented a statement at the International Mineral Dressing Congress in London (1952) indicating that 1) for large particles, the law of Kick was approximately correct; 2) for finer particles, von Rittinger's suggestion was nearer to the truth; and 3) Bond's new

Jan 1, 1961

By M. Semchyshen, A. P. Coldren, W. G. Scholz

A survey of the Fe-Mo-B system was made to determine the extent to which boron might affect the microstructure and strength properties of iron-rich Fe-Mo alloys. Seventeen vacuum-induc tion melted ingots were prepared with approximate mo-lybednum contents 01 2, 4, 9, and 19 wt pct and approximate boron contents of 5, 14,50, and 630 ppm by weight. Phases extracted from annealed specimens and identified by X-ray diffraction analysis included E Fe3MO2, Mo2FeB2, and an oxide hazling a diffraction pattern practically identical to that of MnFez04. Three types of alloy strengthening were observed: a) Fe-2 pct Mo-B alloys were hardenable by a bainitic-type transformtion of austenite to ferrile; b) Fe-4 pct Mo-B alloys were hardened by the solid-solution mechanism; and C) Fe-9 pct Mo-B and Fe-19 pct Mo-B alloys were hardened by precipitation of the E Fe3Moz phase. Boron was observed to have a very strong hardening effect in the Fe-2 pct Mo alloys and a mild strengthening effect on the 1200°F properties of the Fe-4 pct Mo alloys. In the Fe-9 pct Mo alloys there was no consistent effect of boron on strength at either room temperature or 1200° F. The Fe-19 pct Mo alloys were so brittle that meaningful tensile or creep-rupture data could not he obtained. No dispersion hardening from borides was recognized in any of the alloys. THE high-temperature properties of iron-rich Fe-Mo alloys were studied by Reiter and Hibbard.' They found that the strength of the alloys increased markedly as the molybdenum content was raised from 0 to 15.9 pct by weight. The authors explained the various degrees of strengthening in terms of a) solid-solution strengthening, b) strengthening from a martensitic-type transformation, and C) precipitation strengthening. The objective of the present investigation was to conduct a survey of the iron-rich portion of the Fe-Mo-B system to determine whether the beneficial effects of molybdenum on the strength of iron can be enhanced by the presence of boron. It was thought that perhaps fine dispersions of molybdenum- rich borides would be found which could improve the high-temperature strength of ferritic alloys beyond the strengths attainable by molybdenum additions alone. Also, it was considered worthwhile to study the effects of boron in alloys which are essentially free of carbon. Most, if not all, of our present knowledge about boron in high-temperature alloys pertains to alloys containing carbon and carbides. EXPERIMENTAL PROCEDURES Alloy Preparation. Seventeen 8-lb ingots were prepared from electrolytic Plastiron, unalloyed molybdenum chips, and boron powder by a vacuum-induction melting procedure employing hydrogen as the main deoxidizer. The alloys were melted in alumina crucibles using 35-lb melts, with each melt being split four ways to achieve varying boron contents within four Fe-Mo base compositions. The results of chemical analyses conducted on chips machined from the chilled ends of the ingots are presented in Table I. The boron analyses were performed by a spectrographic method utilizing primary standards prepared from boric acid. They indicated that in ingots to which no boron was

Jan 1, 1964