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By G. L. Simard, D. J. Salley, J. Chupak

DITHIOPHOSPHATES and xanthates are the principal collectors for sulphide minerals, and consequently any knowledge of mineral-collector systems of this type is of value. In the present investigation an attempt was made to obtain information on the interaction of a typical dithiophosphate with galena. In carrying out this study, radioiso-topes, so much discussed in the past few years,', ' were extensively employed. By using radioactive dithiophosphate synthesized from radioactive phosphorus, a rapid and sensitive analytical procedure G. L. SIMARD is in the Research Division, Stamford Research Labs., American Cyanamid Co., Stamford, Conn.; J. CHUPAK, formerly in the Research Division, Stamford Research Labs., is now at Camp Detrick, Frederick, Md.; and D. J. SALLEY is in the Research Division, Stamford Research Labs. AlME New York Meeting, Feb. 1950. TP 2815 B. Discussion (2 copies) may be sent to Transactions AlME before April 30, 1950. Manuscript received Oct. 17, 1949. was at hand. This permitted determination of such important quantities as the rate of uptake of dithiophosphate by the mineral, the amount existing at equilibrium on the mineral surface and in the solution, and the desorption of the agent from the surface. Such measurements were possible even on single crystals of galena. In addition the exchange of dithiophosphate between the solution and the sorbed phase was examined, a matter which could be accomplished only by the use of isotopes. It is desired to point out at this time that throughout this paper the term "sorption" has been employed to designate the uptake of agent by mineral, without implication as to the nature of the process by which the uptake was accomplished. Experimental Materials: Galena: The galena was from the Tri-State district. For studies on ground mineral four preparations were used during the course of the investigation. These were prepared from selected large crystals by wet grinding in order to reduce surface oxidation. Alcohol was chosen as a convenient medium for this purpose. The ground mineral was then fractionated by sedimentation in alcohol, dried by evacuation, and stored in a nitrogen-filled desiccator. Data on the preparations are tabulated in table I. The size analysis indicated that the areas of the preparations were of comparable magnitude, even though the absolute values may be somewhat incorrect. Dithiophosphates: Nonradioactive dithiophbsphate (di-isopropyl or di-secondary butyl) was obtained by purification of a commercial product. An aqueous acid solution of the agent was extracted with petroleum ether, the ether layer dried, and the dithiophosphate precipitated as ammonium salt with anhydrous ammonia. Several repetitions of this process resulted in a nearly colorless, flaky product of good purity. (General formula (RO,)PSSNH,). Radioactive dithiophosphate was synthesized by heating radioactive elementary red phosphorus* • For early experiments (1943 to 1944), the elementary red phosphorus was obtained from the cyclotron group at the Crocker Radiation Laboratory of the University of California. Berkeley, through the courtesy of Dr. Joseph W. Hamilton. For more recent work (1946 to 1949). the elementary radioactive Phosphorus has been supplied by the Oak Ridge National Labarotories on allocation from the U. S. Atomic Energy Commission. with sulphur at 270" to 300°C to produce radioactive P,S,. The latter was then treated with the desired purified alcohol (isopropyl or secondary butyl) at 60" to 80°C to form the dithiophosphoric acid derivative. Purification was effected in the same manner as for the nonradioactive material. The effectiveness of the purification method was established by the isotopic dilution method." The same technique was used to show that only negligible decomposition of neutral or of carbonate solutions of the dithiophosphate took place over a period of a day; this was true whether or not galena was suspended in the solutions. Procedures: Radioactivity: The activity of a solution was obtained by counting with a small glass-jacketed, silvered Geiger counter, using a conventional scaling circuit.' Crystals and other solids were counted under a bell-shaped, mica-window counter tube. Sufficient counts were made so that the probable error of counting was of the order of +I-3 pct. The specific activity in terms of counts per minute

Jan 1, 1951

By R. T. Hukki, P. Voutilainen

This paper describes a new apparatus for continuous wet fine-screening. Its preferred size range seems to be from 0.1 to 1 mm. The supercritical trommel screen is a short cylindrical trommel of wedge-bar type construction operated at a speed greater than the calculated theoretical critical speed and at a speed lower than the speed at which particles introduced into it will centrifuge. The paper describes results obtained with the prototype supercritical trommel screen in pilot plant scale. The results point to a high capacity and simultaneously to a high sharpness of screening. Finally, an analysis is presented of the forces acting in screening on a supercritical trommel screen. In the era of high speed, high capacity processing of raw materials the conventional slowly rotating trommel screen is often considered a relic from the times passed. A typical trommel screen is the cylindrical trommel rotated about a horizontal or slanting axis at a relatively low speed. Its screening characteristics are well known. Trommel screens of various types of construction, methods of operation, performances and other characteristics have been described in detail by Taggart.1 The theoretical critical speed of a trommel screen is defined by the same well known equation as that applied for grinding mills: where ncritical = the numerical value of the theoretical critical speed in rpm, D 1 = the inside diameter of the trommel in feet, and D2 = the inside diameter of the trommel in meters. ncritical corresponds also to the centrifuging speed provided that the coefficient of friction f between the trommel surface and the outer layer of the charge is = 1.0. In a general case: From Eq. 2 it is seen that in all cases where f < 1.0 the centrifuging speed of the trommel is greater than the theoretical critical speed. The supercritical trommel screen concerns screening operations within that speed range which is between the theoretical critical speed defined by Eq. 1 and the centrifuging speed defined by Eq. 2, under conditions such that the coefficient of friction f<1.0. It is reported by Taggartl that the optimum speed of a conventional cylindrical trommel screen 36 in. in diam was experimentally found to be about 16 rpm. From Eq. 1, the critical speed of this trommel is 44.2 tpm. The indicated optimum speed corresponds to (16/44.2) x 100% = 36.2% of the theoretical critical speed. The optimum speed range based on information available seems to vary from 33% up to 45% of the theoretical critical value. The trommel screen operated at a supercritical speed: operates at a speed greater than the calculated theoretical critical speed; operates at a speed lower than the speed at which the charge introduced into it will centrifuge; operates within the supercritical speed range in such a way that the coarse fraction of the charge must slide in respect to the inside surface of the trommel; the outer layer of the said fraction next to the screen tends to proceed in the same direction as any selected point on the trommel surface, but now at a lower speed, and indeed at a subcritical speed; allows to a certain degree adjustment of the maximum determining particle size x of the fine product simply by a variation of the speed of the trommel within the supercritical speed range. With increasing trommel speed, finer and finer material only will get the opportunity to find its way into the fine product while the screen opening remains constant. In conventional practice, the low speed trommel is generally used for sizing of coarse and medium coarse material, but seldom for fine screening. The characteristic feature of the product passed through the conventional trommel is that the determining size x of the biggest particle is barely smaller than the nominal size of screen opening. The supercritical trommel screen, on the other hand, is best suited for sizing of relatively fine material. Furthermore, the characteristic determining size x of the biggest particle in the fine product can be substantially smaller than the nominal width of the screen opening or slot. In the trommel screen best suited for the applications

Jan 1, 1965

By A. Stanley, J. C. Mead

The MacIntyre Development of the National Lead Co. is located at Tahawus, N. Y. The operations involve the mining and concentrating of a titaniferous iron ore to produce an ilmenite concentrate and a magnetite concentrate. Construction of the MacIntyre plant was commenced during the summer of 1941,when world conditions threatened to cut off the supply of Indian ilmenite. An open pit mining operation was developed and the crushing and milling equipment put in operation in July 1942. A general description of the operation was given in the Adirondack Issue of Mining and Metallurgy for November 1943. The metallurgy of the mill operation was described by Mr. Frank R. Milliken,* Plant Manager, National Lead Company, MacIntyre Development, and presented at the AIME New York Meeting, February 1948. The magnetite concentrate produced in the milling operation was too fine (minus 20 mesh) to be used directly in iron blast furnace operation, and most of the magnetite had to be stockpiled in 1942 and 1943. In 1943, the Defense Plant Corp. built a Greenawalt sintering plant at Tahawus, N. Y., to put the magnetite concentrate in a more suitable form for use in the iron blast furnace. The Greenawalt sintering plant consists of three 10 by 25 ft sintering pans designed to produce 1800 gross tons of sinter per 24 hr. The vacuum to each pan is produced by two Greenawalt fans in series, pulling approximately 30,000 cu ft of air per minute at 50 in. water gauge vacuum. The plant started operation in August 1944. The present plant production averages 25 tons per operating pan hour (approximately 224 lb per operating hour per square foot of grate area) of plus 1 in. sinter. Raw feed to the plant consists of 61 pct magnetite, 4 pct anthracite coal culm, and 35 pct minus 1 in. return fines which are conveyed to a pug mill where the materials are mixed thoroughly and water added to give the mixture 5.5 to 6 pct moisture. The mixed prepared feed is conveyed to two 4 by 10 ft vibrating screens where the minus 1 in. plus 5/8 in. return fines are screened out and discharged into a surge bin for use as a hearth layer. The minus % in. prepared feed is discharged into another surge bin for use as prepared feed. A charge car, electrically operated, having a capacity of one charge of prepared feed and several charges of hearth layer, lays a thin layer of plus 5/8 in. return fines and 9 1/2 in. depth of prepared feed into the pans. A fluffing roll and a vibrator on the car fluffs and spreads the prepared feed into the pans. An ignition car, electrically operated, ignites the top of the bed with a 30 sec flash burn. The 9 1/2 in. bed sinters in approximately 13 min. Dumping the pan, and recharging and igniting the bed requires 2 min. To improve the quality of the ilmenite concentrate produced in the mill and to reduce the amount of titanium dioxide lost in the mill tailings and in the magnetite product, extensive research work and pilot plant operations have been done on grinding the crude ore to minus 65 mesh size (rather than to minus 20 mesh) and concentrating it by a combination of magnetic separation (for magnetite recovery) and flotation (for ilmenite recovery). These tests have proved successful in increasing ilmenite recovery and grade. With the development of the ilmenite flotation process to a stage where a full scale flotation plant was in the design stage, the problem arose of handling the 65 mesh magnetite concentrate that would be produced. In order to study and solve the problems of handling and sintering the 65 mesh magnetite in the sinter plant, a pilot sinter plant was plus from John E. Greenawalt. The effect of using 65 mesh magnetite in the sintering operations was then studied on the 2.4 sq ft test pan, operating under conditions as similar to the large plant as could be set up in the laboratory. A series of tests were run in the test pan on present sinter plant feed that had been mixed in the plant pug mill. An average production and an average quality of sinter produced in this series

Jan 1, 1950

By Joseph C. Mead, Alan Stanley

The MacIntyre Development of the National Lead Co. is located at Tahawus, N. Y. The operations involve the mining and concentrating of a titaniferous iron ore to produce an ilmenite concentrate and a magnetite concentrate. Construction of the MacIntyre plant was commenced during the summer of 1941,when world conditions threatened to cut off the supply of Indian ilmenite. An open pit mining operation was developed and the crushing and milling equipment put in operation in July 1942. A general description of the operation was given in the Adirondack Issue of Mining and Metallurgy for November 1943. The metallurgy of the mill operation was described by Mr. Frank R. Milliken,* Plant Manager, National Lead Company, MacIntyre Development, and presented at the AIME New York Meeting, February 1948. The magnetite concentrate produced in the milling operation was too fine (minus 20 mesh) to be used directly in iron blast furnace operation, and most of the magnetite had to be stockpiled in 1942 and 1943. In 1943, the Defense Plant Corp. built a Greenawalt sintering plant at Tahawus, N. Y., to put the magnetite concentrate in a more suitable form for use in the iron blast furnace. The Greenawalt sintering plant consists of three 10 by 25 ft sintering pans designed to produce 1800 gross tons of sinter per 24 hr. The vacuum to each pan is produced by two Greenawalt fans in series, pulling approximately 30,000 cu ft of air per minute at 50 in. water gauge vacuum. The plant started operation in August 1944. The present plant production averages 25 tons per operating pan hour (approximately 224 lb per operating hour per square foot of grate area) of plus 1 in. sinter. Raw feed to the plant consists of 61 pct magnetite, 4 pct anthracite coal culm, and 35 pct minus 1 in. return fines which are conveyed to a pug mill where the materials are mixed thoroughly and water added to give the mixture 5.5 to 6 pct moisture. The mixed prepared feed is conveyed to two 4 by 10 ft vibrating screens where the minus 1 in. plus 5/8 in. return fines are screened out and discharged into a surge bin for use as a hearth layer. The minus 5/8 in. prepared feed is discharged into another surge bin for use as prepared feed. A charge car, electrically operated, having a capacity of one charge of prepared feed and several charges of hearth layer, lays a thin layer of plus 5/8 in. return fines and 9½ in. depth of prepared feed into the pans. A fluffing roll and a vibrator on the car fluffs and spreads the prepared feed into the pans. An ignition car, electrically operated, ignites the top of the bed with a 30 sec flash burn. The 9½ in. bed sin-ters in approximately 13 min. Dumping the pan, and recharging and igniting the bed requires 2 min. To improve the quality of the ilmenite concentrate produced in the mill and to reduce the amount of titanium dioxide lost in the mill tailings and in the magnetite product, extensive research work and pilot plant operations have been done on grinding the crude ore to minus 65 mesh size (rather than to minus 20 mesh) and concentrating it by a combination of magnetic separation (for magnetite recovery) and flotation (for ilmenite re-covery). These tests have proved successful in increasing ilmenite re-covery and grade. With the development of the ilmenite flotation process to a stage where a full scale flotation plant was in the design stage, the problem arose of handling the 65 mesh magnetite concentrate that would be produced. In order to study and solve the problems of handling and sintering the 65 mesh magnetite in the sinter plant, a pilot sinter plant was secured from John E. Greenawalt. The effect of using 65 mesh magnetite in the sintering operations was then studied on the 2.4 sq ft test pan, operating under conditions as similar to the large plant as could be set up in the laboratory. A series of tests were run in the test pan on present sinter plant feed that had been mixed in the plant pug mill. An average production and an average quality of sinter produced in this series

Jan 1, 1950

By J. Chupak, D. J. Salley, G. L. Simard

DITHIOPHOSPHATES and xanthates are the principal collectors for sulphide minerals, and consequently any knowledge of mineral-collector systems of this type is of value. In the present investigation an attempt was made to obtain information on the interaction of a typical dithiophosphate with galena. In carrying out this study, radioiso-topes, so much discussed in the past few years,&apos;, &apos; were extensively employed. By using radioactive dithiophosphate synthesized from radioactive phosphorus, a rapid and sensitive analytical procedure G. L. SIMARD is in the Research Division, Stamford Research Labs., American Cyanamid Co., Stamford, Conn.; J. CHUPAK, formerly in the Research Division, Stamford Research Labs., is now at Camp Detrick, Frederick, Md.; and D. J. SALLEY is in the Research Division, Stamford Research Labs. AlME New York Meeting, Feb. 1950. TP 2815 B. Discussion (2 copies) may be sent to Transactions AlME before April 30, 1950. Manuscript received Oct. 17, 1949. was at hand. This permitted determination of such important quantities as the rate of uptake of dithiophosphate by the mineral, the amount existing at equilibrium on the mineral surface and in the solution, and the desorption of the agent from the surface. Such measurements were possible even on single crystals of galena. In addition the exchange of dithiophosphate between the solution and the sorbed phase was examined, a matter which could be accomplished only by the use of isotopes. It is desired to point out at this time that throughout this paper the term "sorption" has been employed to designate the uptake of agent by mineral, without implication as to the nature of the process by which the uptake was accomplished. Experimental Materials: Galena: The galena was from the Tri-State district. For studies on ground mineral four preparations were used during the course of the investigation. These were prepared from selected large crystals by wet grinding in order to reduce surface oxidation. Alcohol was chosen as a convenient medium for this purpose. The ground mineral was then fractionated by sedimentation in alcohol, dried by evacuation, and stored in a nitrogen-filled desiccator. Data on the preparations are tabulated in table I. The size analysis indicated that the areas of the preparations were of comparable magnitude, even though the absolute values may be somewhat incorrect. Dithiophosphates: Nonradioactive dithiophbsphate (di-isopropyl or di-secondary butyl) was obtained by purification of a commercial product. An aqueous acid solution of the agent was extracted with petroleum ether, the ether layer dried, and the dithiophosphate precipitated as ammonium salt with anhydrous ammonia. Several repetitions of this process resulted in a nearly colorless, flaky product of good purity. (General formula (RO,)PSSNH,). Radioactive dithiophosphate was synthesized by heating radioactive elementary red phosphorus* • For early experiments (1943 to 1944), the elementary red phosphorus was obtained from the cyclotron group at the Crocker Radiation Laboratory of the University of California. Berkeley, through the courtesy of Dr. Joseph W. Hamilton. For more recent work (1946 to 1949). the elementary radioactive Phosphorus has been supplied by the Oak Ridge National Labarotories on allocation from the U. S. Atomic Energy Commission. with sulphur at 270" to 300°C to produce radioactive P,S,. The latter was then treated with the desired purified alcohol (isopropyl or secondary butyl) at 60" to 80°C to form the dithiophosphoric acid derivative. Purification was effected in the same manner as for the nonradioactive material. The effectiveness of the purification method was established by the isotopic dilution method." The same technique was used to show that only negligible decomposition of neutral or of carbonate solutions of the dithiophosphate took place over a period of a day; this was true whether or not galena was suspended in the solutions. Procedures: Radioactivity: The activity of a solution was obtained by counting with a small glass-jacketed, silvered Geiger counter, using a conventional scaling circuit.&apos; Crystals and other solids were counted under a bell-shaped, mica-window counter tube. Sufficient counts were made so that the probable error of counting was of the order of +I-3 pct. The specific activity in terms of counts per minute

Jan 1, 1951

By M. G. Benz

The superconducting performmce of diffusion-processed Nb3Sn is influenced by its micro structure. High isotropic transverse current density may be achieved in this material by a process which forms a precipitate of ZrO, within the Nb3Sn. FOR an ideal type-I1 superconductor, little or no transport current can be carried in the mixed state; i.e., little or no transport current can be carried above the lower critical field H,,, where the field penetrates abruptly in the form of current vortices or fluxoids, even though full transition to the normal state does not occur until the upper critical field H,,.&apos; Fortunately, nonideal type-I1 superconductors can be readily obtained and these carry large transport currents up to the upper critical field H. Both theoretical and experimental investigations have attributed this current-carrying capability for nonideal type-I1 superconductors to pinning of the fluxoid lattice by heterogeneities in the microstructure of the superconducting material. These heterogeneities may take the form of dislocations or dislocation clusters,2"5 grain boundaries: structural imperfections introduced by phase transformations; radiation damage,8"10 or precipitates.11"15 Nb3Sn formed by diffusion processing is a type-I1 superconductor. Heterogeneities are needed for high superconducting critical currents above H,,. This paper will cover: a) what the microstructure of diffusion-processed NbSn looks like; b) what changes in the microstructure take place when the system is doped with precipitates, and c) how these changes in microstructure influence the superconducting critical currents. EXPERIMENTAL Preparation of Samples. Diffusion processing was used to form the Nb3Sn. The procedure used was as follows: a) coat the surface of a niobium tape with tin; b) heat-treat this tape at a temperature above 930°C to form a layer of Nb3Sn at the Sn-Nb interface. Such a layer of NbsSn is shown in Fig. 1 The thickness of the NbsSn layer formed was controlled by the time and temperature of the heat treatment. The same general procedure was used for preparation of both undoped samples and samples doped with a precipitate. An additional step was included in the preparation of the doped samples which consisted of internal oxidation of zirconium to form ZrOn. The details of the doping process will be reported in a later paper. Sample Testing. The Nb3Sn tape samples were soldered to a copper or brass shunt. Current and voltage leads were then attached to the sample in the usual four-probe resistance measurement configuration. The sample was cooled to 42°K. In some cases it was cooled in the presence of a high magnetic field and in other cases with the field turned off. The results were the same for both cases. The samples were oriented in a configuration with field transverse to current but could be rotated such that the angle between the field vector and the wide side of the tape sample could be changed. Measurements up to 100 kG were done in a superconducting solenoid and measurements above 100 kG in a water-cooled copper magnet at the MIT National Magnet Laboratory. Once the test field was reached, the current in the sample was increased until voltage was detected across the sample. The critical current was taken as the current at which voltage was first detected in excess of background noise. In most cases this was 1 to 2 x 10~6 v for a— in.-wide sample carrying several hundred amperes with a in. separation between voltage leads and with a 10 "-ohm shunt resistance. RESULTS AND DISCUSSION Microstructure. Examination of the microstructure of the undoped Nb3Sn shows rather large-diameter (1 to 2 columnar grains growing outward from the niobium surface toward the tin surface. As the layer is made thicker by longer diffusion times, these grains grow longer. Few new grains are started. Transmission electron microscopy shows little or no second-phase material within the bulk of the Nb3Sn layer. The microstructure of a diffusion-processed NbsSn layer changes quite drastically when the system is doped so as to form a precipitate within the NbsSn layer. Instead of large-diameter columnar grains of NbaSn forming, smaller-diameter (0.5 to 1 ) equiaxed grains of Nb3Sn decorated with the precipitate form. Fig. 2 shows a transmission electron micrograph of a Nb3Sn layer doped with zirconium oxide. This layer has been etched so that one may look between the grains

Jan 1, 1969

By AIME AIME

ANNOUNCEMENT of the annual meeting to be held Feb. 18 to 22 inclusive will be mailed the latter part of the month to all members. Particular attention is called to the fact that application has been made for reduced rail- road fares on the Certificate Plan. When you purchase your railroad ticket be sure to ask for a CERTIFICATE for yourself and members of your family. Last year over 400 members and dependent members of their families attending the meeting secured return railroad tickets at half price by means of this certificate, thereby saving thou- sands of dollars. Those who fail to obtain this certificate when purchasing going tickets will lose money. Unless 250 certificates are validated at headquarters it will be impossible for anyone to secure the reduced rate.

Jan 1, 1929

AlfreD H. Cowles, Cleveland, Ohio (commuaication to the Secretary*):—Mr.Gillette&apos;s paper and his deductions seem to me of the very greatest importance, if the validity of his conclusions and figures can be confirmed. His work seems to solve an unfinished problem that I attempted to solve on the same lines about two years ago, at a time when I was preparing a paper&apos; on another subject for the American Electrochemical Society. The following paragraph is quoted from the paper referred to: "I feel convinced that a further study of the heats of combination now known for so many compounds, which merely express in other terms their voltages of disruption, will show us the allowance that must be made as a departure from unity in the case of each element, for the intrinsic charge of its elementary molecule, and thereby render possible the creation of a table of apparent relative atomic capacities for electricity, similar to the table of atomic weights. With the numerals of this table known, thermal reaction or energy-transformations will be read with the same ease that we now read and trace the shifting of mass

Jan 1, 1904

By R. J. Reynik

A semiempirial small flunctation theory of diff- sion in liquids is presented, which employs a fluctuation energy assumed quadratic for a small atomic or molecular displacement and Einstein&apos;s random-iralh model. The resulting diffusion equation is given by In these equations. D is the diffusivity, is the average liquid shite coordination number (at interatomic distance d. cm. T is the absolute temperature, xu. em, is (the diffusive displacement. K, is the quadratic fluctuation energy force constant, and rg, cm, are the radii oj diffusing atoms A and B, respectively. The quantities Xn and K are calculated from the computer-filled values of the slope and intercept. respectively. The radius of self-diffusing atom or radii and of diffusing atoms A and B are eta United and compared with values reported in the literature.. The predicted linear variation of diffusivity with. It tempera lure htm been observed in approximately thirty-iire metallic liquid systems, and in over seventy-fiee other liquid systems, including the organic .alcohols, liquified inert gases, and the molten salts, ALTHOUGH the average density within a macroscopic volume element of liquid is constant for fixed total number of atoms. pressure. and temperature, there exist microscopic: density fluctuations within the respective volume element. As such the microscopic volume available to an atom and its Z first nearest neighbors at any instant of time fluctuates above and below the average volume available to these atoms. If one assumes that liquid state atoms vibrate as in a solid. and further postulates that the mean position of any atom in the liquid state is not stationary. but shifts during every .vibration a distance 0 5 j 5 xo. then every atom in the liquid state continuously undergoes diffusive displacements which vary in the range 0 5 j 5 ro. Mathematically. for a binary liquid system consisting of atcrms A and B. the maximum diffusive displacement. .YO, is defined by the equation: where d is the average liquid state interatomic distance at specified liquid state coordination number Z. and v~ \ and vg are the effective radii of diffusing atoms A and B: respectively. For self-diffusion. r^ equals rg , and Eq. [I.] reduces to: It is interesting to note that Eq. [l] or [2] can be used to compute the radii of the diffusing atoms, provided one had an experimental evaluation of xo. As such. the computed radii could be compared with metallic or crystallographic ionic radii to ascerlain the electronic character of the diffusing atoms. Thus it is proposed that in the liquid state the n~otion of an atom relative to its original equilibrium position of oscillation represents the thermal vibration of any atom and its Z first nearest neighbors. while the small and variable displacements. 0 5 1 5 xc,. of the centers of oscillation represent the complex diffusive motions of the atoms at constant temperature and pressure. This is consistent with data obtained from slow neutron scattering by liquids1 &apos; and resembles an itinerant oscillator model of the liquid state.&apos;" It is further postulated that the atomic displacements characterizing the liquid state diffusion process are essentially a random-walk process. As such. it nlay be described by Einstein&apos;s equation:&apos; where D is the diffusivity. sq cm sec-&apos;. j2 is the mean square value of the diffusive displacement. and i> is the frequency of density fluctuations giving rise to diffusion. FORMULATION OF DIFFUSION EQUATION The effective spherical volume occupied by an atom, as a consequence of a microscopic density fluctuation which enlarges the volume available to any atom, exceeds its average liquid state atomic volume by an amount: where AV is the enlarged spherical volume, v is the radius of the diffusing atom. and j is the elementary displacement distance from the original center of oscillation of the vibrating atom to a new center of oscillation position. For small atomic displacements. where c is a constant whose value depends upon the assumed geometry of the enlarged volume. For a spherical increase in volume, c equals 4nr2. Following the treatment of Furthl&apos; and ~walin." assuming the enlarged volu~nes AL7 for the diffusing atoms are distributed in a continuunl. the probability of finding a fluctuation in the size range 0 5 j 5 xo defined by Where c includes the geometric constant cl and Eij) is the fluctuation energy causing the volume change. But the proposed model assumes all the Z first nearest-neighbor atoms are centers of oscillation. and hence the probability that any of these atoms is adjacent to a fluctuation of magnitude 05j5xo is unity. Thus:

Jan 1, 1970

By R. W. Fountain, W. D. Forgeng, G. M. Faulring

Precipitation of the phase Co3Ti (Cu3Au type) from a Co-5 pct Ti a11oy has been investigated using single-crystal X-ray diffraction techniques. Oscillation and transmission Laue patterns of specimens aged for short-time periods at 600" C indicate the formation of titanium-rich and titanium-poor zones coherent with the {100} matrix planes. Longer aging times at 600° C establish that the equilibrium phase also forms on the {100} matrix planes as platelets. These observations are corroborated by electron metallography; electron diffraction studies show the phase Co3Ti to be ordered. A probable sequence of the precipitation reaction is discussed. A previous publication by two of the present authors reported on the phase relations and precipitation in Co-Ti alloys containing up to 30 pct Ti.1 The results of this investigation established the existence of a new face-centered cubic inter metallic phase, ranging in composition from about 17.0 to 21.7 pct Ti at temperatures below 1000° C The decomposition of the fcc supersaturated solid solution was studied employing hardness and electrical resistivity measurements. The changes in hardness upon precipitation in alloys containing 3, 6, and 9 pct* Ti were found to be associated with an initial increase in hardness followed by a plateau and then a second, more pronounced hardness increase. Investigation of this behavior by electrical resistivity measurements suggested that two different kinetic processes were involved, which, when interpreted in terms of the kinetic relation,2-4 indicated that initial precipitation was in the form of thin plates. On continued aging, the plates impinged during the growth process. The general features of these findings have been confirmed by Bibring and Manenc,5 while, in addition, they report the phase to be ordered. The present investigation was undertaken to provide more definite information on the structural relationships between the precipitate and the matrix. EXPERIMENTAL PROCEDURE Single crystals of a (20-5 pct Ti alloy were prepared from the melt employing the Bridgman technique. Poly crystalline rod, 1/2 in. in diam, prepared from vacuum-melted material, was machined to 3/8- in. diam to remove any surface contamination that may have resulted from hot-working. The crystals were grown under a purified hydrogen atmosphere in high-purity alumina crucibles heated by induction. Considerable difficulty was encountered in attempting to grow monocrystals because of the high melting point of the alloy and the high solute concentration. However, one crystal about 6 in. long was obtained which was essentially a single crystal except for one or two very small grains around the periphery. The as-grown crystal was solution heat-treated for 24 hr at 1200°Cin a purified argon atmosphere and water-quenched. One-quarter-in. slices were taken from each end of the solution heat-treated crystal for chemical analyses, and the remainder of the crystal was mounted and oriented by the back reflection Laue Method. The chemical analysis of the crystal was as follows: Pct Ti Pct 0 Pct C Pct N Pct H Pet CO 5.29 0.08 0.004 0.002 0.0003 Balance By proper tilting of the crystal, it was possible to obtain slices 1/32 in. thick of [loo] and [110] orientation. The solution heat-treated crystal slices were sealed in silica capsules for the aging treatments, with titanium sponge placed at one end of the capsule to act as a getter. All slices were water-quenched from the aging temperatures, the capsules being broken under the water to ensure a rapid quench. Thinning of the slices for transmission X-ray studies was accomplished by a combination of mechanical and electrolytic techniques, the final thickness being about 0.1 mm. Laue patterns of the solution heat-treated crystal indicated that no strain was introduced by the thinning technique. ELECTRON METALLOGRAPHY After X-ray examination, the structural changes attending the precipitation were followed by examination of direct carbon replicas of polished and etched surfaces of the single-crystal slices and extracted phases. The earliest indication of significant structural change was observed after aging at 600°C The structure of a heavily etched, solution-treated crystal is shown in Fig. l(a). Aside from the etch pit pattern, no regularity of background structure is observed. On the other hand, in the background of the specimen heated for 500 hr at 600°C, the etching pattern shows a directionality indicating the influence of minute precipitate particles, Fig. l(b). On electrolytic dissolution of this specimen in 10 pct HC1 in alcohol, a large volume of very small, flattened cubes

Jan 1, 1962

By A. H. Daane, J. F. Haefling

The limits of miscibility in some of the uranium rare-earth alloy systems have been determined in the temperature range 1000°to 1250°C. The solubilities of lanthanum and cerium in uranium are greater than those of the remaining rare earths by a factor of more than two. The solubility of uranium is greater in cerium, braseodymium, and neodymium than in the other rare-earth metals studied. The values found in this study are in qualitative agreement with those which might be expected if the solubility rules of Hildebrand and Scott are applicable. AS interest in nuclear reactors intensifies, many new types of fuels are being suggested in attempts to improve the economics of some of the proposed reactor schemes. To remove some of the difficulties inherent in the use of solid-fuel elements and their reprocessing, many types of liquid-metal reactors have been suggested. One of the more attractive features of several of these reactor concepts is that they include a continuous or semicontinuous process for the extraction of fission products and "bred" fissionable materials from the fuel, utilizing immiscible metal extractants. This would enable a much higher burn-up of fissionable material to be achieved and would present a very attractive economic picture. Several studies have been reported on equilibrium systems in which there exists a high degree of immiscibility between uranium and another metal that might be used as an extractant in such a processing scheme.&apos; Two of these systems in which a high degree of immiscibility exists are those of uranium with the two rare-earth metals, lanthanum, and cerium. Since the rare earths constitute a significant fraction of the fission products, their removal is of prime importance. It is reasonable to believe that this might be accomplished by equilibrating a rare-earth phase with the contaminated uranium fuel in the liquid state. In order to make a more complete study of those systems which would be of interest either as extractants in a liquid-liquid extraction process, or as fission products formed in the fuel, the alloy systems of uranium with lanthanum, cerium, praseodymium, neodymium, and samarium were studied in some detail in the temperature range 1000" to 1250°C; less detailed studies were made with the other rare earths. In addition to being of value to the reactor program, the data obtained in this study should be of help in making a study of the role played by the electronic structures of metals in determining the nature of metallic solutions. The unique electronic structures of the rare-earth elements make them particularly interesting in this respect. EXPERIMENTAL The usual procedure for a solubility determination was to seal equal volumes of uranium and the particular rare earth in a tantalum crucible under an atmosphere of helium; this crucible was then sealed in a stainless steel jacket in an atmosphere of helium. These samples were equilibrated by repeated inverting of the crucibles in a furnace for 15 min at the desired temperature, left in an upright position for 15 min to permit separation of the two phases, and then quenched under a stream of water. In some runs the temperature of the furnace was held 50&apos; to 100°C above the desired quenching temperature while inverting in order to insure good mixing. However, it was found that above 1200°C the crucibles were subject to failure and for these runs the furnace temperature was not raised above the desired quenching temperature. A small amount of tantalum was dissolved in the uranium and the rare earths in these runs, a maximum of 3 wt pct in the uranium phase at 1250°C and up to 1 wt pct in the rare-earth phase at this temperature. On cooling, the major portion of this tantalum precipitated as primary tantalum crystals. Any residual tantalum would probably have a negligible effect on the mutual solubility of uranium and the rare earths in each other. Samples for analysis were cut from each phase with an abrasive cutting wheel; the region near the interface between the two metals was carefully avoided. In the case of the rare earths with melting points above 1250°C no solubility data were taken on the rare-earth phase since this phase could not have achieved equilibrium in a reasonable length of time. (For the same reason no data were taken on the uranium phase below its melting point of 1132°C.) Equilibrium appeared to have been reached in the uranium phase in these cases although the rare-earth phase had not melted. To verify this, samples were melted together in an arc furnace similar to that described by Kroll.2 These samples were sub-

Jan 1, 1960

By J. S. FINLAY

OPERATING a "muck stick" never appealed to me. It always seemed a terrible waste of energy to "put rocks in the box" by hand-particularly when my own personal energy was involved. But during the past forty years, there have been periods-more or less extended when I was compelled, against my finer instincts, to muck or quit eating. For about the same length of time, I have devised schemes to make mucking faster and more painless. There was always something mechanically wrong with these designs-too many;" parts to wear out and need replacement, and excessive cost incidental to a complicated mechanism. The idea of a shovel unit comprised of a single, rigid assembly which would roll from a digging to dumping position solved the problem of simplicity and durability. Ingersoll-Rand&apos;s utility engine provided a splendid power plant, small enough and powerful enough for the job. In the machine finally developed, known as the Eimco-Finlay loader, roller chains are preferred to gears for power trans-

Jan 1, 1935

By Robert F. Calman

OUTLINE FIVE EXAMPLES OF GOLD-LINKED FINANCINGS 1. Financing the Lupin Mine • Sale of Cdn $40.0 million of 12% preferred shares and Cdn $40.0 million of Gold Purchase Warrants @ $595 per ounce. 2. Financing the Copper Range acquisition • Borrowing 100,000 ounces from a Canadian chartered bank @ US$307 for five years. 3. Financing the Round Mountain expansion • Borrowing up to US $80.0 million in dollars, convertible into gold, repayable over five years from a group of North American banks. 4. Financing the Tenneco Precious Metals Division acquisition •Sale of SFr 110.0 million of ten year 3-718% bonds with warrants to buy 132,000 ounces of gold at US $560. 5. On Forward Sales, Puts and Calls • Gold, Silver, Canadian Dollars, Swiss Francs THE FINANCIAL RULES AT ECHO BAY 1. Never bet the company 2. Equity is the primary form of capital for a gold mining company 3. On debt 4. The Yardsticks for Corporate Decisions 5. Financial Community Relationships 6. Dividend Policy No Text Available Tables Follow

Jan 1, 1990

By Leonard H. Goldman, Harold E. Marr

The PGT uranium assay probe is a borehole tool developed by Princeton Gamma-Tech over the last several years. It has the ability to do an in-situ assay of uranium in the presence of any amount of disequilibrium. It has some advantages over coring including cost, speed of analysis, and accuracy. In this paper we would like to give a brief description of the measurement and then show some sample logs from South Texas. Uranium exploration and development is carried out primarily by gamma logging since uranium daughters are prolific emitters of gamma rays. The conventional gross gamma tool for uranium logging is limited in value because of the inability of this tool to distinguish uranium from its daughters and other naturally occurring radioisotopes, such as potassium and thorium. This problem becomes severe in cases of disequilibrium. Disequilibrium, in a geological context, is defined as the condition when the gamma radiations from the daughter products are being emitted in a location different from that of the parent uranium. In the decay chain of uranium almost all the gamma radiation emitted in the entire chain comes from the daughter product, bismuth-214. Bismuth-214 is separated from uranium by several long-lived isotopes that are chemically active and have different physical properties, often resulting in shifts in the location of bismuth- 214 relative to the parent uranium. In the United States orebodies exhibiting disequilibrium are a common occurrence and the use of a gross gamma log to delineate uranium orebodies can lead to errors. At present the solution to the disequilibrium problem is extensive coring followed by chemical analyses of the cores. There are several drawbacks in using this technique. First is the high cost of coring, the second is the fact that no results are available for days, or typically, weeks after the drilling is done. Thus for development work, coring and drilling must be done on a grid basis and many additional holes are cored to ensure that the entire orebody is mapped. Another disadvantage to cores is the fact that a small volume is sampled, the volume of the core itself. This leads to problems in the mapping out of the orebody when the ore de- posit is not very homogeneous. The PGT probe described in this paper is a new solution to the disequilibrium problem. Basically, the probe measures radiations that come almost directly from uranium itself. The first daughter of uranium, which is protactinium-234 (Pa-234), is only separated from uranium by a 24-day half-life and no disequilibrium problems build up in such a short time. The PGT probe measures the intensity of a one MeV gamma line emitted by Pa-234 and, using this information, calculates the concentration of uranium. The PGT probe is 24" in diameter and 12 feet long. The probe contains a microprocessor which passes the information to a larger minicomputer in the truck. All data is analyzed on site, and the results from a high speed printer are presented to the geologist. Data is also available on 9- track IBM compatible tape for further processing. The PGT probe output is linear with uranium concentration. The only correction factor is for borehole size, and that only becomes important in boreholes bigger than seven inches in diameter. Dead time is compensated in the probe itself and no problems have been encountered in ore zones up to several percent UjO8. In addition to the uranium assay, a conventional gross gamma log is plotted alongside. Grade thicknesses for zones above cutoff are calculated as well as disequilibrium factors. COMPARISONS During its commercial operation PGT logged a series of 18 holes that had been cored and assayed. All of the holes in this series were logged in normal operation by regular field operators. The time to log each hole was generally under an hour, and in typical operation a PGT logging truck will do between 7 and 8 holes a day. The results of the comparison of the PGT and the core assays are presented in a series of figures showing plots of the PGT assay, core analysis and gross gamma measurements. The first three figures show individual holes with the gross gamma plotted along with the core and the PGT assays. All three logs were from holes on the reduced side of a rollfront deposit in South Texas. In Figure 1 we see the two wings of the roll- front at 143 ft and 150 ft separated by a barren zone. The wings are well defined both by the PGT assay and the core. There is approximately a one foot shift which can be attributed to drilling errors. The gross gamma is showing a rather severe discrepancy, being considerably lower and not showing the barren zone. The grade thickness calcula-

Jan 1, 1980

By Samuel H. Dolbear

THE value of a mine is basically dependent on its capacity to yield profits. Since the ore must be mined, treated, and sold, some of it in various future years. there is a risk involved as to future costs, selling price, and working conditions. It cannot be expected that the economic condition existing at the time of valuation will continue unchanged for long periods in the future. During the past 20 years, mineral production in the United States has been conducted under a changing economy in many respects more exacting than that applied to other businesses. There have been increased production incentives, technical aid, exploration of privately owned mineral deposits by government at federal expense, and liberal loans for development and equipment, with risk partially assumed by government.. Some of these benefits have been counterbalanced by price ceilings, consumption controls, and stimulation of competition from foreign producers who have been offered the same advantages extended to American operators. For the present, mines will operate under a government policy directed toward reducing federal aid and control. The tenure of this change will depend upon future elections and the status of foreign relations. War and threat of war are now of the most vital significance to the mineral industries. Other factors which influence cost of production, markets, and price of mine output might be classified as Acts of God or Acts of Government. In some countries expropriation and the difficulty of exporting earnings or investment returns are risks that must be considered by foreign capital. Recognizing that this retards American investment in foreign countries, the Mutual Security Agency offers insurance against such expropriation and guarantees the convertibility of capital and profits. Since it is impossible to predict with certainty either cost of production or selling prices of metals for long periods, some assumptions must be made as to profits in the future. The basic assumption must be that the price of the company&apos;s product will vary in proportion to changes in operating cost. There is often a lag in this reaction, however, for prices of minerals are generally more sensitive to declines and less sensitive to increases than are costs. This reflects in part the resistance of labor to downward wage revision and a corresponding alertness in realizing its share of price advances. Some labor contracts include automatic adjustments to metal prices. Notwithstanding the complexity of the, problems involved and the difficulty of weighing their effect on value, such risks may be appraised with reasonable accuracy and a rate of earnings adopted that is compatible with the risk. It is, of course, possible to revert to a yardstick of value such as the commodity dollar, which has been advocated from time to time, but while revaluation in 1933 disturbed public confidence, the theoretical gold dollar continues to be the standard of greatest stability. Its gain or loss in purchasing power is reflected ultimately in cost of production and selling price of the mine product. At present 35 dollars are allocated to one ounce of gold. Measurement of Risk In the application of the Hoskold and most other formulae, a yearly dividend rate commensurate with the risk involved is set aside out of annual earnings. If the risk is great, this rate may be 15 to 25 pct of the amount invested. The remainder is placed in a sinking fund invested in safe securities such as high grade bonds or conservative equities, and the interest or dividends from these securities are added to the sinking fund. The sum of these sinking fund payments and the compounded interest at the end of the mine life is taken as the value of the mine. Admittedly the decision as to the size of the risk rate is the most difficult element in valuation and one requiring the most exacting consideration. It is necessary to look years ahead in an effort to determine future costs, market prices, demand, competition which may develop, including that of substitutes, and other influences common to the mine and to the region in which it is situated. Another phase of risk is the enactment of unfavorable legislation, taxes, and what appears to be an alarming spread of nationalization and expropriation. Capital is sometimes borrowed from the government to finance strategic production. Such loans may be collectable only out of production and involve no liability otherwise. Valuation in these cases must recognize the effect of such a reduction in liability. Offsetting some of these risks are the possibilities of mechanization and other cost-reducing discoveries, improvements in mining and treatment methods, new uses for minerals and metals, and normal growth of markets. In this paper, the terms risk rate, dividend rate, and speculative rate are synonymous. Safe rate and redemption rate are also used interchangeably. These alternatives are used here because they are commonly found in the literature on mine valuation. In Michigan, the State Tax Commission has long employed a risk rate of 6 pct in its valuation of iron mines. There the outline of reserves is well established and operating costs and conditions are based on adequate experience. The following comment on rates appears in the report of the Minnesota Interior commission on Iron Ore Taxation submitted to the Minnesota Legislature of 1941.1 Most engineers agree that 7 percent for the specu-lative rate is "an absolute minimum". C. K. Leith in

Jan 1, 1954

By P. L. De Bruyn

The adsorption density of dodecylammonium ions at the quartz-solution interface has been Theadsorptiondensitydetermined as a function of collector concentration and pH. A ten thoushasbeenandfold range of amine salt concentration was covered at neutral pH. Experimental results show that over a thousandfold concentration range at neutral pH, the adsorption density (I) is proportional to the square root of collector concentration. Except at high concentrations, I increases with increases with increasing pH, but in general this effect is surprisingly small. . , . . A critical pH curve has been established for the flotation of quartz with dodecylammonium acetate. The conditions along the flotation curve are correlated with the adsorption measurements. THE behavior of collectors at the mineral-solution interfaces is usually explained in terms of an ionic adsorption process. Through the distribution of collector ions between the solid surface and the- co-existing solution phase the mineral is believed to acquire a water-repellent surface coating. Quantitative adsorption studies have been made on simple flotation systems1-4 only within the last few years. Such investigations were made possible by the adoption of the radiotracer method of analysis. As a consequence of these studies a new parameter has been added to aid the understanding of the flotation process. The research investigation to be discussed in this paper was undertaken to obtain a better understanding of the behavior of a cationic-type collector. This objective was approached through the determination of the distribution of dodecylammonium acetate between the quartz-solution interface and the solution as a function of the collector salt concentration and pH. To bring this investigation to focus on the more practical aspect of flotation research, an attempt was also made to correlate the adsorption results with actual flotation tests. Quartz: A —100 mesh ground crystalline quartz was infrasized; the products of the third and fourth cones were mixed together and reserved for experimental purposes. This stock material was cleaned by leaching in boiling concentrated HC1. After leaching the quartz was rinsed with distilled water until the filtrate showed no trace of chloride ian. It was then washed several times and dried. The qwrtz had a specific surface of 1400 cma per g as deterhined by the krypton gas adsorption method. Collector: The distribution of dodecylammonium acetate between the quartz surface and the solution phase was determined by the radiotracer method of analysis with carbon 14 as the tracer element. The radioactive amine salt with C" synthesized into the hydrocarbon chain5 was supplied by Armour and Co. The tracer element was located adjacent to the polar group. The radioactive salt as received had a specific activity of about 0.14 mc per g. When desired, dilution of this activity was effected by addition of non-radioactive dodecylammonium acetate also supplied by Armour and Co. ........ All other inorganic reagents used in this research were of reagent grade. Conductivity water was used for making up all solutions. Adsorption Tests: Two different experimental methods were used. In the first, to be designated as the agitation method, a weighed amount of quartz and a measured volume of amine salt solution were agitated in a 100-ml or 50-ml glass-stoppered pyrex graduated cylinder. The cylinder was filled with solution up to the stopper, since erratic results were obtained when an air space was left over the suspension. Time of agitation varied from 1 to 2 hr. Preliminary tests at different agitation times showed that the amount adsorbed remained constant for all agitation times exceeding 1/2 hr. After this conditioning period, the solids were separated from the solution by filtration through a Buechner fritted-disk funnel. The solution was re-circulated 10 times or more to allow the fused silica disk to come to equilibrium with it. Determinations of the amount of amine adsorbed on the frit itself indicated that this amount was less than 10 pct by weight of the amine acetate abstracted by 10 g of quartz. The funnel with quartz covered by a thin layer of solution was then centrifuged for approximately 5 min, at which time the moisture content of the solids was reduced to about 5 pct by weight. The wet quartz was blown into a tared beaker, re-weighed and allowed to dry at room temperature. A final weighing was then made to determine the moisture content. The second experimental method, similar to the procedure adopted by Gaudinand Bloecher,&apos; will be referred to as the column method. Two liters of solution were passed through a bed of quartz contained in a Buechner funnel attached to a pyrex separatory funnel by means of a ball and socket joint. Preliminary tests showed that increasing the volume of solution above 2 liters does not give a measurable increase in adsorption. From 4 to 4 1/2 hr were required for 2 liters of solution to pass through the column. The moisture content of the quartz was again reduced to a minimum by centrifuging. A slightly modified column apparatus was used for experimenting with alkaline amine solutions. The same basic unit was used, but the underflow from the Buechner funnel was again fed into a Separafory

Jan 1, 1956

By J. E. Lawver, J. D. Raulerson, Charles C. Cook

The agriculture industry has made great strides during the past decade to increase agriculture yields through increased use of fertilizers. Increased use of fertilizers may prevent, or at least delay, mass starvation due to the alarming increase in world population. Phosphate was added to soil as a plant nutrient in the form of calcined bones at least 2000 years ago (Anon., 1964), and man has used phosphate minerals as a source of fertilization in one form or another for at least 100 years. During 1977 the world produced about 116 Mt of phosphate rock, with about 86% used for fertilizers and another 4% for animal feed supplements. More than three-fourths of the total production comes from the United States, Morocco, and the Soviet Union. From a mineral beneficiation point of view, the major sources of phosphate rock and the methods of beneficiation can be classified as follows: marine deposits not containing appreciable carbonate minerals, marine deposits requiring a francolite carbonate mineral separation, igneous deposits not containing appreciable carbonate minerals, and igneous deposits requiring apatite carbonate mineral separation. [ ] Guano, mostly from Chile and Peru, accounts for 0.1% of the total world production, and the calcium phosphates from Ocean, Nauru, and Christmas Islands and the aluminum and iron phosphates from Brazil and Aruba account for less than 4% of the world production and are thus not considered in this classification (Lawver, et al.). At present, marine phosphorite deposits account for about 75% of the world&apos;s production; the igneous deposits account for 20%. The igneous deposits low in carbonate minerals are easily concentrated by crushing, grinding, and apatite flotation. The most important igneous deposits are those of the Kola Peninsula, USSR (Woodrooffe, 1972). The igneous deposits high in carbonate materials are of corn appreciably more difficult to beneficiate, but they have been concentrated by froth flotation for a number of years. An interesting but rather complicated flowsheet of this type is at Phalabonva, in the Republic of South Africa (Lovell, 1976). The Phalaborwa deposit is an igneous complex of pyroxenite with a central core of carbonatite surrounded by a serpentine- magnetite-apatite rock called phoscorite. The phoscorite containing about 10% P2O5, 35% magnetite, and 35% calcium magnesium carbonate is currently being processed. The process involves comminuting the material for fiberation and subjecting it to a copper float using a potassium amyl xanthate as collector and triethoxybutane as a frother followed by a magnetic separation of the tailings to produce a feed for phosphate flotation. This process produces a phosphate concentrate containing greater than 36% P2O5 at a P2O5 recovery ranging from 75 to 80%. Considerable success has been claimed for recovering apatite from carbonate-bearing ores at the Jacupiranga Mine of Serrana S/A (Silva and Andery, 1972). The carbonatite currently being mined contains an average of only 5% P205 and is concentrated using a unique flotation process (Andery, 1968) to yield 96% P205 concentrates. The ore contains about 12% apatite, 5% magnetite, 80% calcite plus dolomite, and minor amounts of phlogopite, olivine, zircon, ilmenite, and pyrochlore. Feed preparation consists of crushing to -31.75 mm (-1 M in.), rod milling in closed circuit with hydrocyclones to about 92% (-50 mesh), and two-stage cyclone desliming of the -50 mesh sands at 20 m. Weight recovery in the deslimed feed is normally 85 to 88% and the corresponding P2O5 recovery is usually about 90%. The deslimed feed is conditioned at 60 to 70% solids for 15 min at pH = 8-10 with 0.6 kg/t of causticized starch for iron oxide and calcite-dolomite depression. The conditioned slurry is diluted to 20 to 30% solids, about 0.2 kg/t of fatty acid or soap collector is added to the conditioner discharge, and the reagentized ore is subjected to rougher-scavenger flotation with additional fatty acid added to the scavenger float. The scavenger concentrate is returned to rougher circuit distributor, and the rougher concentrate froth is subjected to two stages of cleaner flotation to yield a final apatite concentrate analyzing 36 to 38% P205. Flotation recovery of P205 is, in general, above 90% when treating fresh carbonatite. The high-carbonate flotation tails normally analyze 1 % P2O5 or less and are suitable for portland cement production. The marine deposits. Types 1 and 2 of central Florida are representative of enormous reserves of phosphate rock that will undoubtedly account for much of the world&apos;s production in the near future. Until very recently the sedimentary deposits high in carbonate minerals (Type 2) have not been considered reserves due to the difficulty in making a francolite-carbonate separation. Although no commercial plant has yet been built to beneficiate Type 2 ore, laboratory and pilot plant data indicate the process is viable. If so, the reserves of Florida and similar deposits throughout the world will be substantially increased. A discussion of the beneficiation of these two types of sedimentary deposits and the relation of the resulting concentrates to the fertilizer industry of the United States is the subject of this paper.

Jan 1, 1981

By B. H. Kear, S. M. Copley

Stress-stvain curves are presented for Ni3Al (y&apos;) cvystals in several ovientations, deformed in tension and compression at constant displacement rate, at temperatures from 70° to 2000°F. Both the yield stress and wovk havdening increase with temperature, with the magnilude of the effect dependent on ovientation. The yield stress maximum occurs at 1500°F in [001], at 1400°F in [011], and at 1200°F in [111]. The suppression of the yield stress peak in [011] and [111] orientatiorzs is due to the onset of cube slip, rather than octahedval slip, a1 elerated temperatures. The temperature and orientalion dependence of work hardening in nominal single slip orientations corvelates with changes in the CRSS ratio for octahedral slip and cube slip, in agreement with a model for work hardening based on pinning of screw dislocalions by cross slip from an octahedral plane into a cube plane. It is concluded that the unique plastic properties of y&apos; have a decisive influence on both ductility and strength characleristics of y +y&apos; nickel-base superalloys. It has long been recognized that the strength of y + y&apos; nickel-base superalloys depends on the precipitation of the y&apos; phase [basically Ni3(Al,Ti)]. This paper presents new data on the strength characteristics of single crystals of simple y&apos; (Ni3Al), and forms the first step in a systematic program aimed at elucidating the mechanisms of hardening in the complex commercial alloys. 1) EXPERIMENTAL PROCEDURE Single crystals of off-stoichiometric NiA1 were grown from the melt under vacuum by a modified Bridgman method. The melt was poured into a preheated alumina mold and crystal growth was promoted from one end by gradient cooling. The crystals were homogenized by annealing in hydrogen at 2400° F for 72 hr followed by furnace cooling. Chemical analysis of samples taken from several crystals gave an average composition of 88.2 wt pct Ni. Spectrographic analysis gave as the principal impurities in weight percent— Si (0.02), Mg (0.01), Fe (0.02), Ti (0.002), Cu (0.008), and Co (0.03). Tensile specimens with specifications as in Fig. 1 were prepared by a series of operations involving electrical discharge machining, precision grinding, and electropolishing. Compression specimens with dimensions 1/4 by 1/4 by -3/4 in. were prepared in a similar manner, except for the initial shaping operation using a precision cut-off wheel/two-circle goniometer unit to give selected crystal orientations. Specimens were deformed in a Baldwin-Wiedemann testing machine with furnace attachment, using a strain rate of 5 x 10-4 sec-1. The strain measuring device consisted of extension arms attached to the tensile grips (or compression plattens) at one end and leading out of the furnace to an LVDT at the other. Temperature was controlled by a thermocouple placed in contact with the specimen. According to the known phase diagram for the Ni/A1 system,&apos; when an alloy of the specified composition is cooled from the melt, primary y (nickel solid solution) dendrites grow at the expense of the liquid phase, which becomes enriched in aluminum. At the eutectic composition the remaining liquid freezes as a two-phase mixture of y + y&apos; (Ni3Al). Upon further cooling, a solid state transformation occurs, involving the precipitation of y&apos; in the primary dendrites, and the complete transformation of the eutectic mixture to massive y&apos;. The as-cast structure consists, therefore, of y + y&apos; dendrites with interdendritic regions of massive y&apos;, i.e., transformed eutectic, Fig. 2. 2) DISCUSSION OF RESULTS 2.1) Stress-Strain Curves. Fig. 3 shows tensile stress-strain curves for crystals in orientations close to [001] deformed at temperatures from 70° to 2000°F. Both the yield stress and total elongation are strongly temperature-dependent. At 70°F, easy glide is absent, and the work hardening coefficient BIT - G/300. At T > 1500°F, the negative slope of the stress-strain curves is due to pronounced necking in the crystals. The yield stress maximum at 1500° F corresponds with a minimum in the ductility, Fig. 4. The extensive duc-

Jan 1, 1968

By H. A. Jr. Koch, C. A. Hutchinson

Miscible phase displacement of oil from reservoirs has been emphasized in the past few years. The reason for this emphasis lies in the high oil recovery attainable by this process. Removal of capillary effects in the reservoir leads to recoveries approaching 100 per cent in the area contacted by the miscible phase. The miscible slug process is one means of obtaining a miscible displacement. Here a band or slug of I,PG is injected into the reservoir prior to gas injection. The idea is to maintain the band of LPG "wedged" between the gas and oil phases and thus achieve a miscible phase displacement. A second method lor achieving miscibility is through the injection of a gas which is not miscible with the reservoir fluid but which develops a zone of miscibility in [he reservoir through mass trans-ier with the reservoir oil.&apos; This mass transfer results in either an enrichment of the lean injected gas by intermediates from the oil or an enrichment of the oil by intermediates from a rich injection gas or one that has been enriched on the surface by LPG addition. We are interested here in discussing the process in which miscibility is developed at the displacement front by the evaporation of interrnediatcs from the oil phase into the gas phase. This process "builds up" its own slug of miscible material at the displacement front and therefore does not require the injection of LPG to obtain miscibil-ily. Each process has its own area of applicability. Generally, the high pressure gas process is applicable only with reservoir fluids which con-!ain a high concentration of inter- mediates. If the high pressure gas process is technically feasible at pressures less than 4,500 psi, it is probably more desirable economically than the slug process. The slug process has broad applicability in the shallower reservoirs and with reservoir fluids which contain a relatively low concentration of LPG and natural gasoline constituents. This paper deals with some new concepts of the high pressure gas injection process where it is proposed that flue gas can be substituted for hydrocarbon gas without sacrificing our goal of miscibility. MECHANISM Introduction Considerable effort has been devoted to study of the mechanics ot the high pressure gas injection proc-one generalization result-ing from some of these studies was that the composition of the injected gas is relatively unimportant in establishing the miscibility pressure* for a given reservoir fluid. This generalization is correct for the composition range of gases typically encountered in the field. Two such gases are a gasoline plant tail gas containing 85 per cent methane and 15 per cent ethane, and a field separator gas containing 70 per cent methane and 30 per cent heavier components. The most important factor which sets the miscibility pressure in the operation is the reservoir fluid composition, particularly the concentration of LPG-natural gasoline constituents. The injected gas is the agent by which the LPG-natural gasoline constituents are concentrated at the displacing front to create a miscible displacement. Based on these results, it appeared feasible that some inexpensive gas, such as flue gas, might be substituted for hydrocarbon gas for use in the high pressure gas process. A re-examination of the phase relations of the high pressure gas injection process should clarify the principle behind using flue gas (essentially nitrogen) as an injection gas. Three Component Diagram The phase relations of the high pressure gas injection process have been illustrated by the use of the three component diagrams.&apos;," In Fig. 1 we have arbitrarily represented the multi-component reservoir system by three components; methane, ethane through hexane, and heptanes plus. The solid curve ABC is the phase boundary curve. It represents the locus of compositions which have fixed saturation pressure at a fixed temperature; the lower branch AB shows bubble point compositions, the upper branch BC, the dew point compositions. Point B is the coniposition of the critical mixture at this temperature and pressure. The dashed lines (tie lines) connect vapor and liquid compositions which are in equilibrium. Let us consider Reservoir Fluid D which we wish to displace in 21 miscible manner by gas injection. Let us further restrict the discussion to the case where miscibility between an injection gas and the reservoir fluid at the displacement front is developed by gas enrichment in the reservoir. For this case, any gas whose composition lies between Points C and E on the right side of the three component diagram can be used to give a miscible displacement of Reservoir Fluid D. This is true because the more mobile injected gas moves faster than the displaced oil and is in continuous contact with virgin oil at the displacement front. This leads to a continuing enrichment 01&apos; the gas at the displacement front by evaporation of the C, - C,

By D. M. Metcalf

MOST PEOPLE think of peat as an inferior substitute for coal as a fuel, and will be surprised to learn that it is extensively mined in this country for use as fertilizer rather than as a fuel. Some years ago the Florida Humus Co. began producing it at Zellwood, Orange County, Fla., in a small way for local use. When, however, the company secured an Institute member, M. H. Cuise, to apply his wide experience in mining to the problems here it was found possible to decrease production costs 70 per cent and increase output tenfold. The obvious way in which to decrease costs was to replace shovel-and- horse methods with machinery, much of which, in order to keep down-invested capital, was improvised by remodeling second-hand equipment, changing the design where necessary to meet the special conditions involved.

Jan 1, 1932