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By D. T. Peters, S. Floreen

The age hardening behavior of an Fe-8Ni-13Mo alloy was studied after the matrix had been varied to produce either ferrite, cold u~orked ferrite, or nzassive nzartensite. The aging behavior of the cold worked ferrite and murtensite structures were very similar. The martensite aging kinetics were much different from those observed in earlier studies of aging of maraging steels, even though the martensite wzatri.r had the same dislocation structure as those found in maraging steels. The results suggest that the previously observed precipitation kinetics of maraging steels ?nay have been controlled by the nucleation be-haviov, which in turn were dictated by the alloy compositions and the resultant identities of the precipitating phases. IT is well known that the rate of precipitation from solid solution depends not only on the degree of super-saturation, but also on the density and distribution of dislocations in the matrix structure. These imperfections often act as nucleation sites, and may also enhance atomic mobility. 'Thus, the presence of dislocations is important since the type and distribution of precipitates may be determined by them. The precipitate density and morphology in turn affects the mechanical properties of the alloy. A number of studies have been devoted to the precipitation characteristics in various types of maraging steels.'-" These are iron-base alloys containing 10 to 25 pct Ni along with other substitutional elements such as Mo, Ti, Al, and so forth, that are used to produce age hardening. The carbon contents of these steels are quite low, and carbide precipitation is not believed to play any significant role in the aging reactions. After solution annealing and cooling these alloys generally transfclrm to a bcc lath or massive martensite structure characterized by elongated martensite platelets that are separated from each other by low angle boundaries, and that contain a very high dislocation den~it~.~~~~~~~~-~~ Age hardening is then conducted at temperatures on the order of 800" to 1000°F to produce substitutional element precipitation within the massive martensite matrix. Most of the aging studies to date have revealed several common traits in these alloys, regardless of the particular identity of the precipitation elements. Generally hardening has been found to be extremely rapid, with incubation times that approach zero. The agng kinetics, at least up to the time when reversion of the martensite matrix to austenite begins to predominate, frequently follow a AX/~~ = ktn type law, where x is hardness or electrical resistivity, t is the time, and k and n are constants. The values of n are frequently on the order of 0.2 to 0.5, which are well below the idealized values of n based on diffusion controlled precipitate growth models. Finally, the observed activation energy values are typically on the order of 30 kcal per mole, and thus are well below the nominal value of about 60 kcal per mole found for substitutional element diffusion in ferrite. The common explanation of these observations is that the precipitation kinetics are controlled by the massive martensite matrix structure. Thus, the absence of any noticeable incubation time has been attributed, after ~ahn," to the fact that the precipitate nucleation on dislocations may occur without a finite activation energy barrier. The low values of the activation energy are generally assumed to be due to enhanced diffusivity in the highly faulted structure. If this explanation that the precipitation kinetics are dominated by the matrix structure is correct then one should observe a distinct difference in lunetics between aging in a martensitic matrix and aging the same alloy when it has a ferritic matrix. Such a comparison cannot be made with conventional maraging compositions, but could be made with the alloy used in the present study. In addition, the ferritic structure of the present alloy could be cold worked to produce a high dislocation density so that one could determine whether ferrite in this condition would age similarly to martensite. EXPERIMENTAL PROCEDURE The composition of the alloy used in this study was 8.1 pct Ni, 13.0 pct Mo, 0.10 pct Al, 0.13 pct Ti, 0.012 pct C, bal Fe. The alloy was prepared as a 40 lb vacuum induction melt. The heat was homogenized and hot forged at 2100°F to 2 by 2 in. bar, and then hot rolled at 1900°F to $ in. bar stock. The aging lunetics were followed by Rockwell C hardness and electrical resistivity measurements. Samples for hardness testing were prepared as small strips approximately 2 by $ by 4 in. thick. Electrical resistivity was studied on cylindrical samples approximately 2 in. long by 0.1 in. diam. The method for making the alloy either martensitic or ferritic was based on the fact that the alloy showed a closed y loop type of phase diagram. At high temperatures, above approximately 24003F, the alloy was entirely ferritic. Small samples on the order of the dimensions described above remained entirely ferritic after iced-brine quenching from this temperature. In practice, a heat treatment of 1 hr in an inert atmosphere at 2500°F followed by water quenching was used to produce the ferritic microstructure. These samples were quite coarse grained and usually en-

Jan 1, 1970

By W. E. C. Eustis

In September last I had my attention called by Mr. R. G. Leckie to a deposit of nickel in the township of Orford, province of Quebec. In many ways it has proved to be a subject of great interest. As this ore is, as far as I can learn, entirely new in mineralogy and metallurgy, it has seemed to me that it would be a matter of interest to the Institute to have laid before it, in a short paper, the peculiarities I have met with in studying it. This deposit of nickel was first described by Dr. T. Sterry Hunt, our President, in the Geology of Canada, 1863, p. 738, in the follow ing terms: " The general diffusion of nickel throughout the magnesian rocks of the Quebec group has been already noticed. It has, however, never been met with in any considerable quantities in these rocks, although workable deposits of its ores may reasonably be looked for

Jan 1, 1879

E. O?C. Acker Jinzoc Adachi Truman H. Aldrich Walter H. Aldridge Anson W. Allen John H. Allen William R. Appleby W. Lawrence Austin W. S. Ayres David Baker John Henry Banks Henry C. Banon Alonzo F. Bardwell Walter A. Barrows H.C. Bellinger Wm de L. Benedict Robert Bentley John F. Berry Andrew A Blair George D. Blood Charles A. Bohn Walter M. Brodie Elwin F. Brown Fredrick Burbidge H.H. Burden Charles Butters

Jan 1, 1944

By S. S. Cole, D. L. Armant

The smelting of titaniferous ores for the past hundred years has not been successful because of thickening of the slags in the furnaces. The interest in the utilization of these iron bearing materials has been due to the extensive deposits which have been found in various parts of the world.1 The literature contains references2 to the use of titaniferous ores in blast furnaces. None of these attempts has met with success due to the lack of sufficient information as to the cause of failures and to economic considerations. Evaluation of the published information, as to the probable cause of failure in various attempts, has indicated that the presence of lower valence titanium oxide and formation of titanium carbide contributed to the failure. It was apparent that severe reducing conditions which are present in a blast furnace had been one of the factors for such failures. The previous smelting operations had as a primary objective the recovery of iron from these ores. Under these conditions the highest recovery of iron could only occur with severe reducing conditions. Application of Melting Point Data The application of the melting point data, from the system CaO-MgO-Al2O3-TiO2 reported in another paper,3 to the smelting of titaniferous ores required an extrapolation of these melting points due to the presence of other impurities from the ores. Likewise, a study of the effect of varying FeO and reduced titanium content of the slag was necessary before the data could be fully applied. The melting point data under oxidizing conditions had clearly indicated that a fluid slag with a melting point in the temperature range of 1370°C could be obtained. The smelting of a titaniferous ore had as a primary objective the production of a high titanium slag which was fluid and substantially free of iron and low in trivalent titanium. Since production of a high titanium slag was of primary importance, rather than the recovery of iron from these ores, the smelting concept could be altered to a marked degree. The ferrous oxide could be maintained at higher levels than is the normal practice in iron ores slags without being detrimental to the slags, although a loss in iron recovery resulted. During the reduction of the molten mixtures of ferrous iron and titanium, carbon acts as the reductant for changing the valence of the titanium and iron. The reaction can go further than in the case of the reduction which occurs in iron-titanium solutions. The formation of metallic iron removes iron from the system, so that the titanium oxide can be reduced to trivalent and divalent titanium oxides and also form titanium carbide which removes the titanium from the slags as a soluble constituent. The problem, therefore, resolves itself into maintaining the proper amount of ferrous iron in the slag thereby avoiding the formation of appreciable amounts of trivalent titanium and no divalent titanium oxide or titanium carbide. The latter two have been found in the viscous

Jan 1, 1950

By W. E. C. A. B. Eustis

(Read at the Philadelphia Meeting, February, 1878.) IN September last I had my attention called by Mr. R. G. Leckie to a deposit of nickel in the township of Orford, province of Quebec. In many ways it has proved to be a subject of great interest. As this ore is, as far as I can learn, entirely new in mineralogy and metallurgy, it has seemed to me that it would be a matter of interest to the Institute to have laid before it, in a short paper, the peculiarities I have met with in studying it. This deposit of nickel was first described by Dr. T. Sterry Hunt, our President, in the Geology of Canada, 1863, p. 738, in the following terms : "The general diffusion of nickel throughout the magnesian rocks of the Quebec group has been already noticed. It has, however, never been met with in any considerable quantities in these rocks, although workable deposits of its ores may reasonably be looked for

Jan 1, 1878

New York Meets first Wednesday after first Tuesday of each month. DAVID H. BROWNE, Chairman. PERCY E. BARBOUR, Vice-Chairman. A. D. BEERS, Secretary, 55 Wall St., New York, N. Y. C. A. BOHN, Treasurer. Boston Meets first Monday of each winter month. W. E. C. EUSTIS, Chairman. - R. L. AGASSIZ, Vice-Chairman E. E. BUGBEE, Secretary-Treasurer, Mass. Inst. of Technology, Boston, Mass. ALBERT SAUVEUR, H. L. SMYTH. Columbia Holds four sessions during year. Annual meeting in September or October. STANLY A. EASTON, Chairman. FREDERIC KEFFER, Vice-Chairman. LYNDON K. ARMSTRONG, Secretary-Treasurer, P. O. Drawer 2154, Spokane, Wash. D. C. LIVINGSTON. FRANK A. ROSS.

Jan 12, 1916

By Zay Jeffries

Discussion of the paper of ZAY JEFFRIES, A. H. KLINE and E. B. ZIMMER, presented at the New York meeting, February, 1916, and printed in Bulletin No. 108, December, 1915, pp. 2359 to 2369. ZAY JEFFRIES, Cleveland, Ohio.-The original portion of this paper represents a laboratory method for determining grain size in metals. It was developed not so much to find a quick method as it was to facilitate certain work which I was carrying on a couple of years ago. I had a great many determinations to make and the planimeter method was very slow, as was the Heyn method, and both of them were laborious, so I tried to shorten the time of the determinations. Since preparing the present paper, Dr. T. M. Focke, Professor of Mathematics at Case School of Applied Science has called my attention to the fact that both the Heyn and Intercept methods are mathematically

Jan 5, 1916

By Beverley S. Randolph

The coal-measures of George's Creek coal-region, in Maryland, lie in a comparatively flat synclinal basin, about 4 miles wide. The dip of the measures is, in places near the edge of the basin, as much as 20 feet in 100. The Pittsburgh seam, known locally as the " Big Vein," is the only seam worked at the present time. Ocean No. 3, one of the large mines of the Consolidation Coal Company, has its opening on the outcrop of the Pittsburgh seam, in a ravine which cuts into this seam to such an extent as to bring this opening to within a mile of the axis of the basin. After working all the coal to the rise of this point, the mine was further developed by extending a slope down the dip of the seam, making such an angle with the line of greatest dip as to give a grade varying from 1 to 10 per cent., down which the empty cars carry a rope from a single-drum winding-engine. The coal was worked from each side of this slope in successive Iifts during its progress. From the top of the slope, for a distance of 4000 feet to the fourth lift, the " make " of water is drained by gravity through a heading into the adjoining mine. Below this point the water was pumped into this same heading, at the fourth lift, from which point, as before mentioned, it flowed by gravity.

Jan 1, 1895

[Alphabetic Section (Page 689): The letter immediately following the member's name indicates grade: M-Member, A-Associate, J-Junior. The numerals following member's grade indicate year of election. The letter following year of election indicates primary Divisional affiliation: A-Mining & Exploration F-Coal B-Minerals Beneficiation G-Petroleum C-Iron and Steel H-Industrial Minerals D-Extractive Metallurgy J-Council o f Education E-Institute of Metals K-Council o f Economics]

Jan 1, 1961

E. O?C. Acker Jinzoc Adachi Truman H. Aldrich Walter H. Aldridge Anson W. Allen John H. Allen William R. Appleby W. Lawrence Austin W. S. Ayres David Baker John Henry Banks Henry C. Banon Alonzo F. Bardwell Walter A. Barrows H.C. Bellinger Wm de L. Benedict Robert Bentley John F. Berry Andrew A Blair George D. Blood Charles A. Bohn Walter M. Brodie Elwin F. Brown Fredrick Burbidge H.H. Burden Charles Butters

Jan 1, 1943

By B. H. Lehnhard, C. J. Cecil

The paper describes the use of the Electric Pilot in the Permian Basin for making permeability surveys of wells and for the selective acidization of wells. A general summary of the information obtained from the many permeability surveys run in this area is given, and the possible application of this information to reservoir control problems is discussed. The application of the Electric Pilot on specific wells, involving well completion, acidizing and workover operations is also included. Introduction The Electric pilot is a comparatively new tool in oil-producing areas. From the beginning, the possibilities of this new service caught the imagination of many of the oil operators and acidizing engineers. Through the continued and ever increasing use of the pilot during the past year, and the close cooperation of the oil operators who have used this service, the efficiency and utility of the Electric Pilot service has been increased to a point where it is now a well established and recognized service. There are two major uses for the Electric Pilot: (I) permeability survey; (2) selective acid treatments. Permeability surveys are made to determine the thickness of the various permeable sections at the borehole, the vertical position of these zones at the bore hole, and the relative capacities of the various zones. Nomenclature Data obtained from the permeability survey are used to calculate three different indexes that pertain to the volume of fluid injected into the various permeable zones. A nomenclature for these various indexes has been set up, which correspond with the various productivity indexes, except that they are a measure of injected fluid rather than produced fluid. The nomenclature and definition of the indexes used in connection with a permeability survey by the Electric Pilot are as follows: 1. Capacity.—The volume of water injected into an individual permeable zone, in gallons Per minute. 2. Capacity Index.—The volume of water injected into an individual permeable Zone, in gallons Per minute Per pound Per Square inch differential Pressure. 3. Specific Capacity Index.—The volume of water injected into an individual permable zone in gallons Per minute Per pound per square inch differential per foot of thickness of the zone at the borehole. Capacity is the most generally used index, and for planning initial acidizing procedures and most workover jobs it is sufficient. For comparing permeability surveys on the same well before and after

Jan 1, 1945

By G. H. Kesler, J. E. Oberele, C. E. Dryden, J. H. Oxley

Heat-transfer rates were measured in a model of a multifilament vapor-deposition bulb fo the preparation of high-purzty metals. Local transfer coefficients for heat transfer frow the filaments to the circuates process stream were determined as a functiol of gas flow rates and bulb, inlet, and filament, geowzetvies. These results a-e then convertted to n mass-t7,ansfer basis to provide a method of correlating vapor-deposition rates and to predict the performance of commercial urzits. The firm1 cor?,elating equation for mass transfer was found to be- wheve k, is the mass-transfer coefficient; D, is bze gas difficsivity : P is the system pressure; R is the gas constant; T is the gas temperature; Df, DB, and Di ave tlze diameters of the filament, bulb, and inlet, respectively; k is the gas conductivity; C, is the specific heat of the gas, M is the wzolecular zleight of the gas; Npr . N,,, NRe a7'e the Prandtl, Schmidt, and Reynolds numbem of the system, respectively; LB is the height of the bulb; and SB and Sf are the total suyiace area of the bulb and filaments, respectively. ONE of the more conventional methods of preparing very high-purity metals is the vapor deposition of the metal upon heated filaments. The reactions which can be employed in such a process generally fall into two classes: 1) Pyrolysis of a volatile metal compound. Generally because of their instabilities, metal iodides are used; however, other metal halides and hydrides have been employed. These processes are frequently carried out under vacuum conditions, and the filaments are maintained at high temperatures. 2) Hydrogen reduction of a volatile metal compound. A metal chloride is normally the preferred feed for these processes, but other halides are sometimes used under special conditions. These hydro- gen-reduction processes are usually operated at atmospheric pressure. Many of the current processes for the production of semiconductor materials are actually vapor-deposition processes. However, the vapor-deposition process itself is relatively old, and almost all metals can be prepared in a state of very high purity by the use of vapor-deposition techniques. Loonam has recently given an excellent review of the iodide process for metal deposition,' and Owen has started some detailed studies with a carbonyl system.' A more general treatment of all vapor-deposition processes has been outlined by Powell, Campbell, and Gonser.3 Despite the fact that vapor-deposition techniques have been employed since 1890, there is a surprising lack of fundamental information regarding the transport characteristics of even the simplest deposition system, the heated filament. The purpose of the investigation described in this paper was to extend some of the earlier data obtained at Battelle to predict deposition rates and the uniformity of deposition in large-diameter, multifilament deposition bulbs under forced convection conditions.4'5 A number of other investigators have already presented a simplified treatment of the deposition process under non-flow conditions, i.e., pure diffusion.6"9 To obtain information on the transport characteristics of a deposition bulb, a model of a typical plant deposition unit was constructed, and local heat-transfer coefficients from the filaments to a circulating air stream were determined under various conditions of air-flow rates and bulb, inlet, and filament geometries. These results were then converted to a mass-transfer basis, and consequently provided a method to correlate experimental vapor-deposition rates and to design commercial deposition units. EXPERIMENTAL WORK Description of Model. The apparatus which was used in this work was a scaled model of one type of deposition bulb. It was constructed of Lucite and was easily altered to give several combinations of diameter of bulb liner, inlet size and location, number of filaments, and outlet geometry. The model is shown in Figs. 1 and 2. The bulb shell was made octagonal for convenience in construction and observation, and the bulb liners were cylindrical. Air, introduced through one of several different jet inlets, was used as the test fluid in these model studies. Filaments for deposition of metal were simulated by metal rods 1/4-in. in diam. Two of the rods could be heated by passing electrical current through them ¦ while the remaining rods could not be heated. This procedure minimized the amount of heat which was

Jan 1, 1962

By C. G. Dunn, F. W. Daniels, M. J. Bolton

IN recent papers on interface energies in metals¹,² the concept of an equilibrium of forces has been used in the measurement of interfacial tensions. Mathematically the equilibrium of three forces is given by the relations: where the 2's are the interfacial tensions (interface energies per unit area of interface) of three phases or grains meeting at angles 21 22 and 23 (212 relates to the 1-2 boundary formed by grains 1 and 2;223 to the 2-3 boundary, etc.). If these relationships are valid, one can calculate relative values of the interface energies from measured boundary angles on specimens which have been brought to equilibrium. Since Eq 1 may be derived through a mathematical process of minimizing the grain boundary energy under the restriction that the ?'s be independent of boundary orientation: the concepts of surface tensions and equilibrium of forces are not particularly essential. To deal with the general case involving dependence of boundary energy on boundary orientation, it becomes desirable to drop certain concepts formerly held (namely that energy per unit area is identical with force per unit length or surface tension) and to use the energy concept alone. It is appropriate, therefore, to use E in place of ? in deriving and using the more general equations that express the anisotropic nature of the grain boundary energy. Herring3# ' recently has derived the required general equations using the principle of minimization of energy. Specifying the boundary orientations in terms of angles (4) measured with reference to crystal axes within the grains, Herring's equations take the form E23 + E21 cos?8 + E12 cos?2 — sin ?12 + sin?2-?E12/?12 =O [2] where the partial derivatives are measured in the direction of counterclockwise rotation of the boundaries. Eq 2 implies that an infinitesimal displacement of the triple point along the 2-3 boundary produces no change in the boundary energy. Similar equations apply for infinitesimal displacements along each of the other two boundaries. From such equations Herring obtains the following general relationship (1 + E1 E2) sin?8 + (E2 — E1) cos?3 ________ E38______________ = (1+ E2 E8) sin ?1+ (E3— E2) cos ?1 __________^5____________[3] (1 + E sin ?2, + (E1 — E8,) COS ?2 1 E28 where E1 = 1/E23- E25 and PC and c8 have similar expressions. It is apparent that Eq 3 reduces to Eq 1 when the c's vanish. Eq 3 also reduces to Eq 1 when the E'S are all equal. Shockley and Read' have pointed out one limitation to these equations. When E plotted versus 4 appears as an energy cusp, as their theory requires, for example, for the energy near a twin boundary position, then Eq 3 (and therefore Eq 1 also) no longer applies if one boundary is in the minimum energy position. One of the equations of form Eq 2, however, applies if the infinitesimal displacement is along the boundary associated with the energy cusp. From the foregoing treatment it will be apparent that equilibrium angles alone are not sufficient in general for calculating relative interface energies.

Jan 1, 1951

By L. E. Snow, L. F. Pett

AT the Utah Copper Pit of Kennecott Copper Corp. a versatile mobile drill unit has been developed and tested. Through increased drilling speed and additional available drilling time, an improvement of 233 pct in drill performance has been realized. Operators using drill power can quickly and easily convert the unit from a vertical to a toe hole drill. Drilling is done with the machine in line with the unit or at right angles to it. Table I covers the 1950 drill record at the mine, showing the types of machines used and the footage obtained. [ ] Development of the new units was prompted by a desire for solution of the following problems: 1-The ever-expanding operations within the Utah Pit, requiring some 65 miles of transmission pipe lines radiating from a central compressed air plant, have now taxed this compressor plant beyond capacity. While 100 lb per sq in. pressure is maintained at compressors, transmission losses from innumerable small leaks result in low terminal pressure at the drills. Fig. 1 illustrates that while terminal pressure varies according to size of air hose and fittings used, the average drill is operating on air pressures within the 60 to 70-lb range. The compressor plant is operated primarily for air rock drills. All drilling is done on day shift, but it is necessary to run two of the three 3720 cu ft capacity compressors during night shift in order to prevent drastic loss of pressure through leaks. On day shift all three compressor units are operated at capacity, so that there is no reserve safeguard available for extensive repairs to any compressor. The calculated volume of compressed air required for operation of 25 drills is but 33 pet of three day-shift compressors. While compressed air is being used to a minor extent for purposes other than drilling, it is felt that satisfactory substitute facilities could be provided in the event that air lines were no longer available. 2-Drill performance has increased beyond the capacity of present 3 ½ -in. drifter machines. 3-The installation, maintenance, and moving of air lines in routine mining is a growing problem. The 2-in. level lines are placed outside electrification towers and must be moved to new location upon completion of each shovel cut. In addition to these moves it is often necessary to dismantle level lines so that excessive shovel spillage, or material covering track following a blast, can be pushed in the clear with bulldozers. Where level room is limited, it is often necessary to remove air lines in giving bulldozers room to prepare grades for wagon drills. In spite of precautions taken, many level lines become buried, twisted, and constricted, with excessive air loss resulting. Excessive back break in blasting often leaves several sections of air line suspended in mid-air. Occasionally air lines come in contact with defective electric transmission towers, so that holes are burned through pipe. 4-Rail-handling of drilling equipment such as wagon drills from one location to another requires considerable locomotive crane crew time. Any new unit developed should travel under its own power. 5-Present practice requires accessory material including hose, water pressure tanks, water barrels, drill steel, and bits to be transported by means of push cars when drill locations are changed on any level. 6-In order to supply numerous drill locations with material, many stock piles of new drill rods, drill bits, and other essentials must be left at strategic points, usually in the vicinity of powder magazines. This practice makes for poor housekeeping and contributes to the loss of supplies. Planning the Unit It was felt that a mobile drill unit which would rectify the foregoing problems should meet certain demands: 1-It must furnish compressed air to operate a 4-in. rock drill at a pressure of 90 to 100 lb.

Jan 1, 1952

By Richard W. Brummett, Robert L. Dubms

Located some 180 miles east of Los Angeles in Riverside County, California, the Eagle Mountain mine supplies iron ore concentrates for the Kaiser Steel Corporation steel plant in Fontana, California, and for export to Japan. Although the deposits were first discovered in the early 1890's, no production was realized from the area until 1948 when Kaiser Steel Corporation commenced operations. A part of the large Basin and Range province, the Eagle Mountain area's geologic column comprises a thick series of metasediments resting on Precambrian gneisses and schists that have been intruded by sill-like masses of porphyritic quartz monzonite. The metasediments are composed of three quartzite units that are separated by a schistose meta-arkose and by two ore zones. They have been folded into a large east-west trending anticlinal structure that extends completely across the Eagle Mountains. The iron ore deposits occur in two well-defined horizons in the metasedimentary series, and they are found only along the north limb of the major anticline. Host rocks for the ore zones were a series of limestones and dolomites with associated quartzites. Magnetite plus pyrite comprised the primary mineralization that formed many replacement lenses and stringers of ore within the ore zones. The primary ore has been oxidized to hematite and goethite in a broad zone at higher elevations in the deposits. Hydrothermal alteration formed actinolite- tremolite granofels, local phlogopite, and minor tourmaline in the ore zones. This alteration and the ore deposition seem related to the same magmatic event that formed the porphyritic quartz monzonite intrusion

Jan 1, 1968

By P. R. Celmer, Leonard R. Weisberg

THE principle of fractional crystallization has been successfully used to prepare high-purity (99.999 pct) Ga. Hoffman and Scribnerl removed single crystals of gallium solidifying in a gallium melt, while Zimmerman2 grew single crystals from the melt by the Kyropolous technique. In contrast, attempts at purifying gallium by zone refining have been less successful. ichards, reported that despite the passage of 40 zones through a gallium ingot, there still remained 5 to 70 ppm each of Cu, Fe, Ca, Mg, Si, Al, and Ag. Previously, Detwiler and Fox4 detected only one impurity, Pb, segregating in zone-refined ingots. These surprising results prompted an investigation of the factors controlling impurity segregation in gallium. Possible reasons for this were insufficient diffusion of impurities in the melt; recontamination of the melt by its oxide film which is not affected by the passage of the zone; reaction of gallium with the boat; sudden freezing of gallium following supercooling, especially since gallium easily supercools to and trapping of impurities at grain boundaries. Impurity segregation tests were carried out by directionally freezing gallium using the Bridgman rnethd, modified in that the molten gallium is lowered out of a furnace into a slush of dry ice and trichloroethylene, thus minimizing supercooling. Since the gallium is contained vertically, the oxide film is in contact only with the tail end of the melt. It was found that Teflon makes an excellent crucible for gallium since it is quite pure, non-reactive, translucent, flexible, machinable, and is not wet by gallium. The gallium crystals could be grown at various speeds, and the melt could be vigorously stirred by a Teflon rod moving through the gallium in a vertical reciprocating fashion. Single crystals could be grown by placing a solid Teflon plug at the bottom of the melt drilled out in such a way to cause the solidifying gallium to follow a winding path. Thus, even if many crystals are originally nucleated, only one grain will predominate. The grain structure of the gallium crystals was revealed by an etchant composed of equal volumes of HC1, HNO3 and HF, diluted with water to half strength. Emission spectrographic analyses were carried out on samples removed from the front and tail ends of the resulting gallium ingots. Typical results of this study are summarized in Table I. The rate of freezing in all three cases was about 1 in. per hr. It can be seen that even though stirring of the melt does help, it is even more important to grow a single crystal of Ga in order to obtain good segregation of impurities. The effect of crys-tallinity on the segregation of impurities was previously observed6 in the directional freezing of germanium; however, in this case, the effect was much less pronounced. This dependence of impurity segregation on the crystalline perfection of Ga may be related to its thermal conductivity which is the most anisotropic of all metals.7 The anisotropic thermal conductivity can cause the solid-liquid interface to be nonuniform, thus leading to trapping of impurities during freeing, and therefore reduced segregation. In conclusion, it is indicated that zone refining of gallium would be more successful if seeding and similar precautions are taken to insure single crystal growth. The authors are indebted to Mr. H. H. Whitaker for the spectrographic analyses and to Drs. B. Abeles and F. D. Rosi for helpful advice and encouragement throughout the course of this work. This research was supported by the Electronics Research Directorate, Air Research and Development Command, under Contract No. AF33(616)-5029. REFERENCES 'J. 1. IToffmon and B. T. Scribrer: I. Research h'atl. Bur. Standards, 1935, "01. 15, p. 205. 'W. Zirnmerman: Science, 1954, vol. 119, p. 41. %J. L. Richards: Nature, 1956, vol. 117, p. 182. 'D. P. Detwiler and W. M. Fox: I. Metals, 1955, "01. 7, p. 205. 5P. W. Bridgman, Proc. Am. ilcod. Sci., 1925, vul. 60, pp. 305,385,423. "S. L1. Christian: private c ommuni cation. 'K. W. Powell: roy. Sac., 1951, vol. 209, p. 525. 'W. G. Pfann: Zone Re fining, p. 20. John Wiley and Sons, Inc., New York, L058.

Jan 1, 1962

By C. R. Sandberg, N. Stein, L. D. Wiener, E. B. Elfrink

this paper presents the results of a study of the slip velocity of gases rising through liquids in vertical tubes, inclined tubes, and vertical annuli. The data were obtained in gas-liquid systems which included combinations of air, propane and natural gas (over 97 per cent methane) with water, lubricating oils, and crude oils. The 214 data points obtained in this study along with 11 data points reported in the literature are incorporated in an empirical correlation which relates the mean slip velocity of gases flowing through liquids with the parameters gas rate, tube size, ratio of liquid viscosity to liquid density, gas density, liquid density, and the angle of the tube from the vertical. The average numerical deviation of the measured slip velocity data from values obtained from the correlation is 9.2 per cent. The average algebraic deviation between measured and Predicted data is 0.31 per cent, an indication that the correlation is a satisfactory representation of the data. The correlation presented in this paper will be useful primarily in the design of subsurface gas-oil separation equipment for increasing the efficiency of oil-well pumping installations. but may perhaps be extended to other situations of gases rising through liquid columns. INTRODUCTION The production of oil by pumping is often complicated by the presence of free and dissolved gas in the oil at bottom-hole conditions. This gas can be drawn into the pump barrel and result in "vapor locking" the pump, thus reducing the efficiency of the pumping operation. Large amounts of free gas may be excluded from the pump by the use of a gas-anchor, which is designed to allow the separation of free gas from the oil before it is drawn into the pump. The design of a suitable gas-anchor depends on a knowledge of the difference between the velocity of the free gas and that of the oil as the oil travels down toward the pump intake. This rate of gas rise through the oil is termed "slip velocity." AS a first step toward the full understanding of this roblem, the mean slip velocities of gases flowing through static

Jan 1, 1952

By H. G. Dwyer

CONSIDERATION for future expansion influenced the design of the new smelter at Chuquicamata. The section of the smelter now going into operation, while large, represents only little more than half of the ultimate plant. Equipment for the direct smelting of raw concentrates has been arranged in the conventional manner although needless details have been eliminated wherever possible while mechanical and electrical features not usually found in copper smelters have been incorporated. Access is afforded to all equipment but platforms and walkways have been held to a minimum. The poling and other platforms in the converter aisle, normally subjected to battering by ladles and other heavy equipment in transit, are of concrete construction with steel grid armor embedded in the exposed surfaces. Noticeably absent are the many platforms formerly required for the handling of converter flux since this material is charged to the converters through the side walls of the converter uptake hoods. Clear space with ample headroom is provided under each converter and converter puncher's platform to permit clean-up by small bulldozers. Remote controls have been introduced at many points. Electrical control rooms and control centers have been conveniently located. An electrical tunnel with cross tunnels and escapeways is situated under the entire length of the converter aisle for power feed lines. Skull breaking facilities are in a separate building near the smelter. A silica-slurry building with brick storage area is adjacent to the smelter building so that elevator service is available to both buildings. A smelter office, a change house and lunchroom are provided in convenient locations. Units of the smelter as presently constructed are shown in the plan and table on page 1194. The ultimate smelter will house 7 reverberatory furnaces, 14 waste-heat boilers, 9 Peirce Smith converters, 4 casting furnaces serving 2 casting wheels, and one holding furnace serving a straightline casting machine. Additional crane requirements in the converter aisle will necessitate the installation of special hoisting equipment in space already provided in a raised section of the roof over the casting end of the aisle. Thus a complete crane may be lifted high enough above the crane rails to permit the passing of another crane underneath thereby giving all cranes full use of repair facilities already installed. For the collection of gases, 2 dust chambers, each with separate stacks, will collect converter gases and 2 balloon flues with separate stacks will collect reverberatory furnace gases. Extensions necessary to complete the ultimate plant will be possible with little interruption to normal operations since the future converters and reverberatory furnaces will be added at the east end while additional casting facilities will be added at the west end of the present plant. The future units may be added singly or all at one time depending on requirements.

Jan 1, 1952

By J. H. Collier

The mother lode, or mineralized belt, at Angels, in Calaveras county, California, is 3 miles wide. At least, a region of that width has been, and is being, prospected which has shown considerable mineralization. The lode proper divides into three lodes, or groups of veins, at this point. On all of these branches, mines have been operated with more or less success.

Jan 1, 1900

By Harvey T. Kennedy, Charles R. Olson

In many investigations of the performance of petroleum reservoirs the assumption is made that the liquid, if below its bubble-point pressure, is at all times in equilibrium with gas. On the other hand, observations by numerous investigators have indicated that gas-liquid systems including hydrocarbon systems, may exhibit supersaturation to the extent of many hundred psi in the laboratory. Up to the present, there has been no reliable data on which ti judge the actual extent of supersaturation under conditions approaching those existing in petroleum reservoirs. The work reported here deals with observations and measurements on mixtures of methane and kerosene in the presence of silica and calcite crystals. Bubbles were observed to form on crystal-hydrocarbon surfaces in preference to the glass-hydrocarbon interface or to the body of the liquid. Statistically, it was found that the number of bubbles formed per second per square centimeter of crystal surface was a function of the supersaturation only. and the function was evaluated graphically. Supersaturations were observed up to 770 psi, under which condition bubbles formed quickly and with considerable violence. With decreasing degrees of supersaturation, the frequency of bubble formation became less, until at 30 psi supersaturation and lower, no bubbles were observed to form, even though the observation at 30 psi was continued for 138 hours. It was found that silica and calcite crystals had identical effects, within experimental error, in accelerating the formation of bubbles, and that small amounts of water and crude oil had no effect on the results. It is shown that the maximum supersaturation that can exist in a reservoir may be calculated from the data presented and from the area of the rock surface. It is also shown that the number of bubbles formed in the reservoir, in order of magni- tude, may be calculated for any rate of pressure decline imposed on the reservoir by production. The bearing of the number and distribution of bubbles on reservoir performance is discussed. INTRODUCTION A liquid system is supersaturated with gas when the amount of gas dissolved exceeds that corresponding to equilibrium at the existing pressure and temperature. The degree of super-saturation may be conveniently expressed as the difference between the bubble-point of the mixture and the prevailing pressure. Thus, if a mixture having a bubble-point of 1,000 psi at a given temperature exists in single liquid phase at 700 psi at the same temperature. it is supersaturated to the extent of 300 psi. There are many examples of high supersaturations, mostly in aqueous solutions, reported in the literature. Thus, Kenrick, Wismer and Wyatt1 showed that water may be saturated with oxygen, nitrogen or carbon dioxide at 100 atmospheres, and the pressure reduced to one atmosphere without producing bubbles immediately. When liquids are in a state of tension, they may be considered as supersaturated at least to the extent of the tension. The tensile strength of water has been reported as 30 atmospheres by Meyer,1 60 atmospheres bv Budgett. 30 to 50 atmospheres by Temperley and Chambers,4,5 200 atmospheres by Dixon6. and 223 atmospheres by Briggs.7 Vincent8,9 determined the tensile strength of a mineral oil as 45 psi. Gardescu1 maintained pressures for short times in a model reservoir at 115 psi below the bubble-point. It should be noted that the high supersaturations observed were obtained on systems carefully purified to remove particles or surfaces which might promote the formation of bubble; These "nuclei" were considered as contaminants which interfered with the determination of a property of the liquid. In

Jan 1, 1952