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By W. L. Hill, W. H. Armiger, S. D. Gooch

The physical properties, chemical behavior under thermal treatment, and fertilizer value of fluorine-containing pseudowavellite (hydrous calcium aluminum phosphate) that occurs as phosphate clay admixed with quartz sand in an extensive deposit near Bartow, Fla., were determined by experiments in laboratory, pilot-plant, and greenhouse. When the mineral was heated at 500°C, 80 pct of the phosphorus become citrate soluble. The heated product, however, deteriorates markedly under moist conditions such as obtain in the soil. EXTENSIVE beds of a soft aluminiferous phosphate lie in the Bartow-Pembroke region of Florida. Although the extent of the deposit is unknown, it is thought that the equivalent of at least five million tons of material containing 25 pct P,Os exists on one large mine property alone, and soft phosphates similar in nature are known to occur elsewhere in the state. This aluminum phosphate, unlike fluorapatite, is rendered fairly soluble in neutral ammonium citrate solution merely by heating it at a temperature below 600 °C, a property made the basis of a process patent by the junior author.' The possibility of producing an available form of phosphorus from what has hitherto been a worthless natural phosphate prompted the Bureau of Plant Industry, Soils, and Agricultural Engineering to make a brief study of the Pembroke phos- phate during the war years with a view towards determining the optimal temperature for heat treatment and the reactions involved in the process. The results of this study supplemented by data and information furnished by the junior author are presented in this paper. Description of Natural Phosphate: The phosphate with admixed quartz sand and siliceous matter occurs as a low-grade (8 to 9 pct P2O5) clay-like material that can be beneficiated cheaply by making a water separation of the very fine material from the sand, floating off the fine material, settling the suspension to a thick slurry, and finally de-watering the slurry by vacuum filtration followed by drying. The product dried at 100 °C contains about 16 pct water and 25 pct P2O5, about 1/12 of which is citrate soluble. Partial analyses of representative samples of the crude ore and corresponding concentrate are given in table I. The concentrate is light yellow in color and even after being dried at 100°C sticks very noticeably to laboratory grinding and screening equipment. Under the microscope the ground material is predominantly light brown crystalline aggregates with index of refraction near 1.61. The principal phosphate mineral constituent was identified as pseudo-wavellite with admixed phosphosiderite.2 Pseudo-

Jan 1, 1951

By W. L. Hill, W. H. Armiger, S. D. Gooch

The physical properties, chemical behavior under thermal treatment, and fertilizer value of fluorine-containing pseudowavellite (hydrous calcium aluminum phosphate) that occurs as phosphate clay admixed with quartz sand in an extensive deposit near Bartow, Fla., were determined by experiments in laboratory, pilot-plant, and greenhouse. When the mineral was heated at 500°C, 80 pct of the phosphorus become citrate soluble. The heated product, however, deteriorates markedly under moist conditions such as obtain in the soil. EXTENSIVE beds of a soft aluminiferous phosphate lie in the Bartow-Pembroke region of Florida. Although the extent of the deposit is unknown, it is thought that the equivalent of at least five million tons of material containing 25 pct P,Os exists on one large mine property alone, and soft phosphates similar in nature are known to occur elsewhere in the state. This aluminum phosphate, unlike fluorapatite, is rendered fairly soluble in neutral ammonium citrate solution merely by heating it at a temperature below 600 °C, a property made the basis of a process patent by the junior author.' The possibility of producing an available form of phosphorus from what has hitherto been a worthless natural phosphate prompted the Bureau of Plant Industry, Soils, and Agricultural Engineering to make a brief study of the Pembroke phos- phate during the war years with a view towards determining the optimal temperature for heat treatment and the reactions involved in the process. The results of this study supplemented by data and information furnished by the junior author are presented in this paper. Description of Natural Phosphate: The phosphate with admixed quartz sand and siliceous matter occurs as a low-grade (8 to 9 pct P2O5) clay-like material that can be beneficiated cheaply by making a water separation of the very fine material from the sand, floating off the fine material, settling the suspension to a thick slurry, and finally de-watering the slurry by vacuum filtration followed by drying. The product dried at 100 °C contains about 16 pct water and 25 pct P2O5, about 1/12 of which is citrate soluble. Partial analyses of representative samples of the crude ore and corresponding concentrate are given in table I. The concentrate is light yellow in color and even after being dried at 100°C sticks very noticeably to laboratory grinding and screening equipment. Under the microscope the ground material is predominantly light brown crystalline aggregates with index of refraction near 1.61. The principal phosphate mineral constituent was identified as pseudo-wavellite with admixed phosphosiderite.2 Pseudo-

Jan 1, 1951

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Jan 1, 1938

By Charles H. Fettke

The Bradford field of northwestern Pennsylvania and adjacent portions of New York state has attracted world-wide attention in recent years on account of the remarkable success that has been attained in the application of water-flooding as a means of increasing the extraction of oil from a pool that had almost reached the economic limit by ordinary production methods. It is one of the few large oil fields in which artificially conducted water drives have thus far proved successful, although many attempts have been made to apply them elsewhere. As detailed a knowledge as possible of the character of the producing sand in this field is therefore of considerable interest, not only from a scientific but also from a practical standpoint. Outside the Bradford field, such knowledge should aid operators in determining whether or not their sands are amenable to flooding. In the Bradford field itself flooding operations are not uniformly successful over the approximately 85,000 acres of productive area, due in many instances primarily to variations in sand conditions. A knowledge of just what these variations are would often be a great aid in overcoming the difficulties, or else would save considerable sums of money which might otherwise be wasted in experimenting in areas where the chances of success are very small. Realizing that more precise information in regard to the nature of the reservoir rock was essential to improvements in the methods of oil recovery, the Northwestern Pennsylvania Oil Producers Assn., by private subscription of its members, took a core of the Bradford sand from a well 1/2 mile west of Custer City, Pa., during the spring of 1925. The Forest Oil Co. also took a core of the same sand from a well about 8 miles east of Bradford at that time. The cores were submitted to the United States Geological Survey for study and A. F. Melcherl has published the results of porosity determinations on the Custer City core.

Jan 1, 1929

By Robert Peele

TWO outstanding members of the Institute will be honored at the Annual Meeting this month: Robert Peele, who will accept his election to the small group of Honorary Members; and Clinton Hoadley Crane, president of the St. Joseph Lead Co. and William Lawrence Saunders Medalist for 1936. Eminence in the profession character, interest in Institute activities, and general recognition as a gentleman and a friend by so many people, have contributed to the election of Professor Peele. The Saunders Medal is for "achievement in mining." In awarding it to Mr. Crane the citation reads "For distinguished achievement in the successful development and operation of low-grade lead mines."

Jan 1, 1936

By R. F. Dickerson, D. A. Vaughan, A. F. Gerds

ALTHOUGH the metallurgy of uranium has been under intensive study since the early 1940's, no systematic effort has been made to identify the non-metallic inclusions in uranium. Uranium carbide (UC), which is probably the most common inclusion found in graphite-melted metal, has been tentatively identified by previous investigators, but the other nonmetallic inclusions have received little attention. Since metallography is a valuable tool in metallurgical studies, the metallographic identification of the nonmetallic inclusions in uranium is important. Such an investigation has been completed and the identification of slag-type inclusions and of uranium monocarbide, uranium hydride, uranium dioxide, uranium monoxide, and uranium mononitride is described. Metallographic Preporation It is often possible to prepare specimens for metal-lographic examination equally well by several methods. The specimens which were examined in this work were prepared by one of two acceptable methods. For the convenience of the reader, both methods will be discussed in detail and will be referred to simply as Method I or Method II in the subsequent sections. For both Methods I and 11, specimens for microscopic examination usually were mounted either in bakelite or in Paraplex room temperature mounting plastic. Method I—Specimens were ground in a spray of water on a revolving disk covered successively with 120-, 240-, and 600-grit silicon carbide papers. It was necessary to perform the final grinding operation carefully on worn 600-grit paper to keep the scratches as fine as possible. After washing and drying, the specimens were polished for 3 to 4 min on a slow speed wheel (250 rpm) covered with a medium nap cloth. Diamet Hyprez Blue diamond polishing paste, Grade 00, 0 to 2 µ, was used as abrasive with kerosene as lubricant on the wheel. Specimens were washed thoroughly in alcohol and final polished electrolytically in an electrolyte composed of 1 part stock solution (118 g CrO, dissolved in 100 cm3 H2O) with 4 parts of glacial acetic acid. A stainless steel cathode was used. At an open circuit potential of 40 v dc, a polishing time of 2 sec retained inclusions well with the bath at room temperature. If additional etching was required to sharpen the interface between the metal and the inclusions, an electrolyte composed of 1 part stock solution (100 g CrO3 and 100 cm8 H20) and 18 parts glacial acetic acid was used at room temperature. Best results were obtained by etching for from 10 to 15 sec at 20 v dc in the open circuit. Surfaces obtained by this method are suitable for microscopic examination. However, if desired, they may be etched further with other chemicals. Method 11—Rough grinding was done on a wet 180- or 240-grit continuous grinding belt. The specimen was then ground by hand successively on 240-, 400-, and 600-grit silicon carbide papers in a stream of water. Final polishing was accomplished on a 4 in. high speed wheel (3400 rpm) covered with Forstmann's cloth. Linde B levigated alumina, suspended in a 1 volume pet chromic acid solution, was the abrasive. Specimens usually were polished in 5 min or less by this technique. Often the inclusions present in the metal were identified in the mechanically polished condition. When etching was required to outline inclusions more sharply, one of the two following methods was used. In the first method, the specimen is etched lightly while electropolishing in the chromic-acetic acid solution described above (1 part of stock solution to 4 parts of acetic acid). The electrolyte was refrigerated in a dry ice-ethyl alcohol bath and specimens were etched at 60 v dc on the open circuit for 2 or 3 cycles of 3 to 4 sec each. The second technique utilizes electrolytical etching at about 10 v dc (open circuit) in a 10 pet citric acid solution at room temperature. X-Ray Diffraction Technique The major problem in the identification of inclusions in metals by X-ray diffraction techniques is the extraction of a sufficient amount of each type of inclusion to obtain an X-ray diffraction pattern. In the present study, X-ray diffraction patterns were obtained from individual inclusions of the order of 10 µ diam. The polished and etched samples shown in the micrographs were examined at a magnification of X54 or XI00 with a binocular microscope. This allowed sufficient working distance to extract the inclusions with a needle probe for powder X-ray diffraction analysis. Friable inclusions such as MgF2, CaF2, UO2, and UH3 could be freed from the metal by probing the as-polished and etched surface. The fine particles then were picked up on the end of a Vistanex-coated glass rod (0.002 in. diam) which was held in a brass adapter made to fit the powder X-ray diffraction camera. The end of the glass rod was centered in the path of the X-ray beam. In the case of the UC, UO, and UN inclusions which are smaller in size, more metallic in appearance, and less friable than the other inclusions, it was necessary to etch the inclusion in relief before extraction. UN inclusions etched sufficiently in relief in the electrolytic polishing solution described in Methods I and II by increasing the polishing time. UN inclusions were relief etched by extending the

Jan 1, 1957

By E. J. Rapperport, E. D. Levine

The boundaries of the (a +ß) field in the Al-Li system were determined between 150°and 550°C utilizing quantitative metallography and lattice-parameter measurements. The solubility of lithium in aluminum decreases from 12.0at. pct Li at 550°C to 5.5 at. pct Li at 150°C. P Al-Li is saturated with aluminum at 45.8 at. pct Li and has this boundary value constant over the temperature range 150°to 550°C. THE solid solubility of lithium in aluminum has been determined by several investigators, 1-6 but, as shown in Fig. 1, there is little agreement among the various determinations. The earliest investiga-tions'-' are suspect because of the use of impure materials. Although high-purity materials were employed in more recent work,4'5 the experimental techniques may have led to contamination of the specimens. Probably the best work has been that of Costas and Marshall,6 who obtained close agreement between results obtained by two independent phase-boundary techniques: electrical resistivity and mi-crohardness. No detailed studies of the solubility of aluminum in the bcc ß phase, Al-Li, have been reported. Cursory investigations1,2,6 have indicated only that the (a+ß) -p boundary lies between 40 and 50 at. pct Li and is relatively independent of temperature. The present work was undertaken in order to provide an independent check on Costas and Marshall's determination of the solubility of lithium in aluminum, to extend knowledge of this solubility limit to temperatures below 225°C, and to make an accurate determination of the solubility of aluminum in Al-Li. EXPEFUMENTAL Alloy Preparation. In view of the difficulties encountered in previous investigations of the A1-Li system, close attention was paid to the use of methods of alloy preparation and treatment that would minimize contamination. Aluminum sheet (99.99 + pct Al) was vacuum-induction melted in a beryllia crucible to remove hydrogen. Lithium (99.9 pct Li) was charged with pre-melted aluminum into a beryllia crucible, in a helium-filled drybox. The crucible was sealed in a Vycor tube and transferred from the drybox to an induction furnace. Melting of alloys was performed by induction heating in a helium atmosphere. Solidification was accomplished by means of a suction apparatus, shown in Fig. 2, in which the alloy was forced by changes of pressure into a 3/16-in. inside diam closed-end beryllia tube. This technique produced rapid solidification of a small portion of the melt, resulting in alloys with a high degree of homogeneity. Typical lithium distributions are presented in Table I. Transverse sections 1/8 in. long were cut from the alloy rods, and each section was split in half longitudinally. One half of each section was analyzed for lithium, and the opposing halves were employed for phase-boundary determinations. Lithium contents were determined by flame photometry with an accuracy of 1 pct of the amount of lithium present. Thermal Treatments. Homogenization and equilibration heat treatments were performed in electrical-resistance furnaces with temperatures controlled to ± 2OC. Calibrated chromel-alumel thermocouples were employed to measure temperature. Homogenization was performed in helium-filled l?yrex tubes for 1 hr at 565°C. The encapsulated specimens were then transferred directly to furnaces maintained at lower temperatures for equilibration. Equilibration times were 2 hr at 550°C, 8 hr at 450°C, 27 hr at 350°c, 90 hr at 250°c, and 285 hr at 150"~. These times were chosen on the basis of conditions employed by previous investigators. Alloys were quenched from the equilibration temperatures by breaking the capsules into a silicone oil bath. By performing all possible operations either in sealed capsules or in a helium-filled drybox, the specimens were given minimum exposure to the atmosphere. Quantitative Metallography. Metallography of Al-Li alloys is difficult because of the atmospheric reactivity of the ß phase. It was found possible, however, to prepare surfaces of good metallographic quality by preventing contact with moisture during preparation. Grinding through 4/0 paper was performed in the drybox. The specimens were then transferred under kerosene to the polishing wheel. Three polishing stages were employed: 25-p alundum with kerosene lubricant on billiard cloth, 1-µ diamond paste on Microcloth, and 1/4-p diamond paste on Microcloth. Between stages the samples were cleaned by rinsing in trichloroethylene and buffing

Jan 1, 1963

By Earl Oliver

SEVERAL notable papers, and free discussion on many controversial subjects, marked the various sessions of the Petroleum Division at the annual meeting. The Division first convened on Tuesday afternoon, Feb. 16, and wound up with a dinner and technical meeting on Thursday night. H. C. Fowler presided at the opening session, which was devoted to problems of engineering research and production engineering. Joseph Chalmers abstracted his paper on the flow of air and gas through porous media, in the preparation of which E. L Rawlins and D. B. Talia-ferro contributed. G. H. Fancher told how much he and his associates at Pennsylvania State College were interested in this field, and described the problems they had met in conducting test work. He made a plea for standardization of testing methods. Mr. Fowler then read an abstract of written discussion by Professor Barb, which was followed by discussion by Dr. Fancher and Mr. Chalmers of technical points in connection with the Chalmers' paper. H. H. Hill abstracted written discussion from Messrs. Wilde and Moore, of the Humble company. The second paper, by K. B. Nowels, on computing pressure drop in the pipe of flowing oil wells, was abstracted by the author. Messrs. Blair Smith, G. W. Coggeshall, and I. I. Gardescu participated in the discussion, and the chairman abstracted written discussion prepared by Mr. Rawlins. Most of this had to do with the viscosity of gas¬oil mixtures, on which subject Mr. Nowels said there was great need of accurate technical information.

Jan 1, 1932

By Don Simon

In the late 1960s the mining industry was in an apparent slump due to a combination of factors. Enrollment dropped significantly at schools offering mining engineering degrees, resulting in a shortage today of experienced mining graduates to staff middle management positions. How has this limited supply affected salaries? Does the shortage impair the mining industry's ability to respond to national energy needs?

Jan 12, 1979

By G. R. Speich

RECENT studies by Smith and Olney,1,2 Olney,3 Greifer and Salli,4 Rys etal., and Olney and smith 6 have established that graphite is the first decomposition product to format the surface of hypereutectoid plain-carbon steels when they are austenitized in a vacuum or inert atmosphere and slowly cooled. This graphite evidently forms directly from the austenite and only at the surface of the specimen. The interior of the specimen is found to be free of graphite. The graphite layer can almost completely cover the specimen surface and the rate of its formation is markedly sensitive to the orientation of the austenite. The present work was undertaken to study this phenomenon further, especially with regard to the effect of temperature and austenite orientation. The material studied in this work was a high-purity iron-carbon alloy containing 0.88 pct C, 0.005 pct Mn, 0.016 pct Si, 0.005 pct S, and 0.002 pct P. Specimens were heat-treated in a commercial hot stage modified for rapid quenching.7 This permitted direct observation of the formation of the surface graphite. A vacuum of 10"" to 10-5 mm of Hg prevented oxidation or decarburization of the specimens. Specimens were austenitized for 30 min at 1100°C and quenched to a series of lower temperatures where they were isothermally transformed. Surface graphite was observed to form at 700°, 750°, and 780°C but not at 825°, 900° or 1000°C. Since the maximum solubility of austenite for graphite is 0.88 pct C at 800°C,8 surface graphite only forms at tem-

Jan 1, 1962

By G. F. Dillion, A. F. Armington

THE present method for the ultrapurification of boron involves the formation, distillation, and decomposition of boron tribromide.' However, the boron tribromide prepared contains several impurities in the ppm range, even after distillation. Some of these impurities, notably carbon, can be reduced after decomposition by zone refining. In this study, a comparison of the purity of boron tribromide at various formation temperatures is presented. The apparatus employed consisted of a bromine flask connected to a 22 mm ID horizontal quartz reaction tube packed with amorphous boron powder, which was in turn connected to a receiving flask cooled with an ice bath. Argon was used as a carrier gas. The approximate rate of passage of bromine to the reaction tube was 25 g per hr. The reaction was first investigated at several temperatures in order to determine the lowest temperature necessary to produce a colorless product which was assumed to be an indication of complete reaction of the bromine. The lowest temperature found in this study was 420oC. The amount of impurities found in the boron tribromide at various formation temperatures is shown in Table I. The data presented are emission spectroscopic results of boric oxide produced by the hydrolysis of 2 to 3 g of boron tribromide in 10 ml of distilled water. After hydrolysis, the samples were dried several hours on a hot plate. Assuming equilibrium conditions in the reactor, one can make approximate thermodynamic calculations estimatling the completeness of reaction of bromine with boron and its impurities at various temperatures. Data for these calculations were taken from Rossini,3 and must be taken as approximations since the T?S factor was not included in the calculations. The results of such calculations indicate that, with the exception of carbon bromina-tion, all impurities would react almost to completeness (> 99 pet) at all temperatures between 400" and 900oC. In the case of carbon, which cannot be accurately analyzed spectroscopically, it is estimated that only about one sixth as much carbon tetrabromide would be formed at 400" than at 900°C. Since some marked reductions in impurity content were observed at the lower reaction temperature which would not be predicted by thermo-

Jan 1, 1962

By C. S. Corbett

There is much comment at present in the ranks of the oil industry regarding unit operation of oil fields and the benefit that would accrue if it could be extensively applied. It seems certain that, as an immediate corrective of the present situation, overproduction could be effectively curtailed with all the advantages of proper conservation of petroleum resources and with no important loss to anyone connected with the industry. Unit Operation in Certain Foreign Fields Many an oil operator in America would doubtless like to have exclusive control of one or more oil-bearing structures for development in accordance with the economic position of the industry and especially in accordance with the best production practice known. A few operators now have this privilege, particularly in certain foreign fields, and are following lines of procedure which show that they are aware of the great opportunity that is theirs. We find in an article by Professor Strigeoff,1 and in a paper read by Captain Comins2 before the American Petroleum Institute, the outlines of procedure adopted, respectively, by the Soviet Government for the nationalized Russian oil fields and by the Anglo-Persian Oil Co. for its fields in Persia. Comprehensive plans for the unit operation of other oil fields may have been described publicly but no such descriptions have come to the attention of the writer. New fields are coming more and more into the hands of single operators or of a few who control large activities and who appreciate fully the need for cooperative action and are willing to forego the lure of a large quick profit from high flush production in order to secure the advantage of better stabilization in the industry and a larger though more deferred profit by operating the field as a unit. Much can be done toward efficient development of an oil field controlled by a few operators who are willing to cooperate for that purpose, but the best result can be obtained only by pooling their interests in the field

Jan 1, 1930

POSITIONS VACANT The National Bureau of Standards needs men to fill metallurgical positions with salaries varying from $1200 to $2000, depending upon the training and experience of the candidate. Experience either in ferrous. or, non-ferrous metallurgy. Duties will be almost entirely of an investigational nature, in connection with problems of military importance. Qualified men are urged to send to the Bureau of Standards at once a statement of training and experience, names of references, acid minimum salary that would be accepted, so that they may he advised of appropriate civil service examination for which to file papers. Until further notice, such papers are received by the Civil Service Commission at any time and ratted promptly.

Jan 10, 1917

By G. M. Schwartz, J. N. Gundersen

John W. Gruner (Professor Emeritus, College of Science, Literature, and the Arts, Dept. of Geology, University of Minnesota, Minneapolis) — It is surprising that two men as well acquainted with the taconite rocks of the Mesabi District as Drs. J. N. Gundersen and G. M. Schwartz should have concluded that the taconite of the Eastern Mesabi before the intrusion of the Duluth gabbro consisted largely of quartz and magnetite. These minerals were "locally reconstituted" into "a wide variety of silicate mineral assemblages" by the gabbro. It is well known, of course, that the silicate mineralogy of the Eastern Mesabi ('about 14 miles in length) is quite different from that of the Main Mesabi which is over 60 miles long. The change from one to the other is abrupt and cannot be attributed to any other cause than the thermal effects of the gabbro. Are we to assume or believe that the taconite of the Eastern Mesabi was radically different from that of the Main range before the gabbro metamorphosed it?

Jan 1, 1962

By John A. Graves

Anaconda's Jackpile-Paguate mine, located between Albuquerque and Grants, N.M., is situated at an elevation of 6000 ft in a semi-arid desert region. The original Jackpile deposit was discovered by Anaconda air and ground exploration parties in Nov. 1951. A large percentage of the uranium mined in New Mexico comes from the Jackpile-Paguate, which is one of, if not the largest, open pit uranium mines in the world. From 1953 to the present, 120 million tons of overburden, mining waste, and low-grade material have been removed to produce approximately 10 million tons of merchantable uranium ore, having an average grade of about 0.25% uranium oxide. Identifying the Orebody Surface drill holes delineate the ore bodies on a predetermined grid which varies in dimension but usually affords 100-ft control. These holes are probed immediately after drilling by geophysical logging trucks, resulting in a gamma log and digital readout from each hole. From this information it is possible to arrive at an almost immediate conversion to percentage of U3O8 on 6-in. intervals. Initially a hole is probed at a reconnaissance speed of 10 fpm with a time constant of 8 sec. Wherever the gamma recording goes off scale on an initial run, that particular zone is rerun at 2 fpm and at a time constant of 2 sec. This time constant is the interval that emissions are counted and accumulated for recording purposes. The search radius of the Geiger probe is approximately 18 in.

Jan 8, 1974

By John V. Beall

The mining industry of Japan is not very large, but it is very old. Some of the mines have 1000 years of history. At Nara, the capitol 1300 years ago, the great Buddha of bronze that was cast at that time was of metal mined from several localities in Japan including the Akenobe-Ikuno district, one of the present Mitsubishi properties. Methods of smelting copper and iron, it is believed, came from China via Korea. A characteristic of the Japanese mining industry today is one of buying abroad and treating at home, a variety of ores of different compositions. All in all, Japan's mineral deposits under its own flag are inadequate for its great industrial strengths.

Jan 5, 1969

By Walter L. Crow

MUCH has been published on highly technical phases of grinding. Very little has been written on how a mill man can improve his operations by determining the optimum size assortment of grinding balls that should be added as a makeup charge. This ball rationing is not to be confused with the ball ration used as an initial charge when the mill is started up. Ball rationing is considered for one or more of the following purposes: 1) to increase throughput of the mill, 2) to reduce the power required per ton of ore ground to the desired size, 3) to reduce steel consumption per ton of ore ground, 4) to improve product size, and 5) to lower retention time of ore in the mill.

Jan 7, 1957

By N. S. Stoloff, J. N. Mushovic

Age hardening response of a Mg-Th-Zr alloy has been studied at temperatures in the range 60° to 450°C. Transmission microscopy revealed clustering of thorium atoms at low aging temperatures, supporting a previous report of GP zone formation. Peak strengthening, which is observed at 325°C, is due to the formation of a coherent, ordered, DO19 type superlattice structure, of Hobable composition Mg3Th, as plates parallel to the matrix prism planes. These plates later reveal a Laves phase structure of composition Mg2Th. The equilibrium Mg4Th phase begins to precipitate in two different forms at an early stage, competitively with the Mg2Th plates. RECENT work on the Mg-Th system indicated that, unlike most magnesium-base alloys, complex precipitation phenomena may be occurring. The partial phase diagram of the Mg-Th system indicates that an equilibrium phase, Mg5Th, is the sole intermediate phase.' sturkey,' however, has reported, using X-ray and electron diffraction techniques, that a metastable fcc Laves phase, Mg2Th, precedes the formation of the equilibrium compound, which he identified as closer in composition to Mg4Th. Murakami et al.3 reported that the equilibrium phase precipitates preferentially on grain boundaries and dislocations in a Mg-1.7 wt pct Th alloy; Kent and Kelly4 aged a more dilute alloy, Mg-0.5 wt pct Th, for 4 days at 220°C and found similar results. In addition, they reported that a platelike phase with a structure close to that of the magnesium matrix forms perpendicular to the basal plane and is probably ordered. Research on a Mg-4 wt pct Th alloy by electrical resistance measurements and transmission electron microscopy has suggested that GP zones may form at low aging temperatures.3 However, the electron micrographs purporting to show this phenomenon were not conclusive. In view of the fragmentary evidence concerning the nature of the precipitation processes in the various Mg-Th alloys, an aging study was undertaken to clarify the characteristics of the various precipitates which form and to correlate the mechanical properties of the system with the direct precipitate-dislocation interactions. The latter results are presented elsewhere.' The purpose of this paper is, therefore, to discuss the precipitation sequence in this system. EXPERIMENTAL PROCEDURE Sheet stock (0.060 and 0.010 in. thick) of a commercial Mg-3.93 wt pct Th-0.42 wt pct Zr alloy (designated HK3lA) similar to that studied by sturkey2 was supplied through the courtesy of Dr. S. L. Couling of Dow Metal Products Co. Zirconium does not enter into any precipitation reactions,' but is present primarily as a grain refiner. The alloy was chill cast, warm rolled to 0.090 in. thick stock, and then finally reduced by a combination of hot and cold rolling. The alloy chemistry is given in Table I. This material was solution treated at 580°C for 4 hr in a dry CO2 atmosphere, and then water quenched. Material in this condition was fairly clear of precipitate particles and was fully recrystallized. Aging at temperatures less than 200°C was accomplished by immersing the alloy in a silicone oil bath; for higher temperatures, aging was done in a salt pot. Age hardening treatments were conducted at 60°, 80°, 105°, 135°, 160°, 250°, 325°, 350°, and 450°C for times ranging from 5 min to 400 hr. Hardness tests were performed on chemically polished 0.060-in.-thick blanks of solution treated material which were aged at the various temperatures for increasing lengths of time. For aging temperatures above 150°C the Rockwell Superficial 30T scale was employed, while samples hardened at temperatures below 150°C were monitored with the 45T scale. Each data point consists of at least three separate readings. Yield stresses also were measured at room temperature on both 0.060 and 0.010 in. sheet specimens aged at 325°C. The aged foils were thinned by the window method in a solution of 80 pct absolute alcohol and 20 pct concentrated perchloric acid (70 pct) maintained at 0°C. A stainless steel cathode was used and the applied voltage was 10 to 15 v. Thinned samples were rinsed in distilled water and pure methanol. After the me-thanol rinse the thin foils were quickly dried between filter paper. Foils prepared by the above method were examined in a Hitachi HU11B electron microscope operating at 100 kv. RESULTS A) Hardness. The hardness data are depicted in Figs. 1 and 2. Peak strengthening occurs at 325°C after aging about 6 min, see Fig. 1. Significant strengthening is achieved also at 350°C, but aging at 450°C produces only softening. The stepped curve at 250°C indicates that a complicated precipitation process may be occurring at that temperature. Fig. 2 suggests that at least two hardening mechanisms exist since the lowest temperature hardness peaks are displaced to the left of the peaks obtained at 135° and 105°C. A great deal of scatter is observed at long times in all cases due to magnesium surface degradation caused by the silicone oil bath. B) Identification of the Strengthening Precipitates. The structure formed atlowagingtemperatures (c10O°C) was not clearly resolvable by transmission microscopy. The only bright-field evidence for a change in structure was a mottled appearance which could be observed at extinction contours, as shown in Fig. 3(a), and the disappearance of this effect when dislocations produced under the influence of the electron beam passed through the matrix, as noted in

Jan 1, 1970

By Harold Margolin

The Ti-Al system certainly merits the investigative attention it has been receiving and this latest contribution by Blackburn is therefore to be welcomed. The titanium-rich end of the phase diagram shown here, as well as the diagram by crossley,17 Clark et a1.,18 and Tsujimoto and Adachi,29 reveal no other intermediate phase than Ti3A1, although a previous work by Ence and Margolin20 had reported an additional intermediate phase. Since then, Buerger Precession pictures of single crystals of 10.5, 11.5, and 12.5 wt pct A1 were made at New York university21 and the extinctions were found to be typical of a D6h a Ti structure. Some superlat-tice spots and/or streaks suggesting the presence of an Mg3Cd structure, i.e., Ti3Al, were also found. Since these specimens had been quenched from the y region20 and had revealed a Ti, it was concludedz1 that y does not exist and the structures interpreted as m + y could not be so considered. The absence of normal two-phase behavior in these structures had been indicated in the paper. Accordingly, the two-phase region y + 6 becomes a + Ti3Al and there is some agreement between the results of Blackburn and of Ence and Margolin20 as to both shape and existence above 900°C of an a + Ti3Al field. Crossley 17 proposed that Ti3Al is a line compound which decomposes congruently at 900°C. It is difficult to discount entirely the fact that clear two-phase structures, varying in amount with position in the two-phase field, could be detected above 900°C by Ence and Margolin.20 Precipitation during quenching could not have been so regular and the twin-phase syndrome17 does not apply. The heat treatment and quenching technique was essentially the same as was used by Crossley, whereas Blackburn, who used a rapid quenching procedure, also showed a two-phase a + Ti3A1 field above 900°C. If the two-phase field exists above 900° C, it is easy to picture a two-phase field which could account for the data of Crossley below 900°C without invoking a line compound existence of Ti3A1. All that would be necessary would be an 0 + Ti3Al/Ti3Al boundary which curved sharply to higher aluminum contents below 900° C. It is clear that the controversy must be solved by techniques which obtain data at elevated temperatures without quenching. It is conceivable that the difference in width of the a + Ti3N fields reported by Blackburn and by Ence and Margolin is due to the longer annealing times used by the latter investigators. The criterion for establishment of equilibrium in our work20 was the

Jan 1, 1969

By Lewis T. Wright

IT is commonly believed by metallurgists that in copper-smelting, the copper in the slags, which is irreducible by continued smelting, is retained in the form of "prills" of matte. I have frequently held well-settled slag in a molten condition for a long period without being able thereby to reduce the copper-content. The slag acted as though it contained a minimum of dissolved or combined copper that could not be settled out by gravity. I have used reagents, but without satisfying myself in what form this copper existed. The same slags, by fine grinding and elutriation, could not be separated into portions containing more or less copper than the average content. By treating copper-slags in an electric furnace an impure button of copper. was produced, but the high temperature and the strong reducing-action of the furnace were influences that suggest an explanation of a result not obtainable with ordinary smelting-temperatures. If all the copper in the slag were in the form of copper-matte, and not existing as a dissolved compound with some of the elements of the slag, then the other metals in the matte, such as gold and silver, should occur in the slag in the same ratio to the copper as to the copper in the accompanying matte. This reasoning led me to study the ratio of metals in the products of smelting, and, apart from the issues discussed in this paper, the research has proved both interesting and illuminative. On the assumption of a similar ratio of metals in matte and slag, if the percentage of copper in the slag accompanying; a matte containing 50 oz. of silver and 1 oz. of gold per ton of copper was 0.3 per cent., or 96 oz. per ton of slag, there should be found 0.15 oz. of silver and 0.003 oz. of gold per ton of slag:; but, in my experience, there is less silver and much

Sep 1, 1909