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By R. F. Mehl, C. E. Birchenall

R. E. Hoffman and D. Turnbull—The authors have presented evidence which they have interpreted as indicating that the rate of self diffusion is not intrinsically more rapid at grain boundaries than within the grain. Grain-size effects which apparently exist are attributed rather to impurities concentrated at the grain boundaries. In view of our own experiments and the existing evidence, we believe that the support for this hypothesis is not convincing. We have in progress an investigation in which the rate of self diffusion of silver is being measured over an extended temperature range in both single-crystal and polycrystalline specimens. The results of the single-crystal experiments and some preliminary data on fine-grained polycrystalline specimens have already been reported:' and it is anticipated that a complete report will be published in the near future. The self-diffusion coefficient of large-grained polycrystalline silver (1 grain per sq mm) has previously been measured by Johnson" between 730" and 940°C. The diffusion coefficients which we have measured in single crystals (210 plane normal to diffusion direction) agree within experimental error with values calculated from an extrapolation of Johnson's curve down to temperatures as low as 500 °C. However, it has been demonstrated that the overall self-diffusion rate in fine-grained polycrystalline specimens (initial grain size of 0.003 cm) becomes measurably larger than the overall rate in a single crystal at a temperature of 600°C, and the discrepancy between the two rates becomes greater as the temperature is further decreased. In fact, it has been possible to obtain satisfactory penetration curves for polycrystalline specimens using the sectioning technique at temperatures as low as 400°C. At this temperature, the penetration is 50 to 100 times greater in the polycrystalline specimens than in a single crystal. Fisher" has developed an analysis whereby the ratio of the rate of the unit diffusion process at the grain boundary to the corresponding rate within the grain can be calculated from the penetration curves and an assumption as to the width of a grain boundary. This analysis applied to our data indicates that the unit process at the grain boundary is faster by a factor of 10' at 475°C when the grain boundary width is taken to be 5. The silver used in most of these experiments was obtained from the Handy and Harmon Co. and listed as 99.97 pct pure. Preliminary experiments on 99.999 pct silver from the Jarrel-Asch Co. indicate a grain-size effect of the same order of magnitude as in the less pure silver. Nominally, these purities are as good, at least, as that of the carbonyl iron used by the authors, but of course if an impurity effect does exist its magnitude might be very dependent upon the nature of both major and minor constituents. The authors have cited the work of other investigators who have found no grain-size effects. Neither Steigman, Shockley and Nix" nor Maier and Nelson8 were able to correlate self-diffusion coefficients of copper with grain size. However, all their measurements were performed at or above 750°C; and on the basis of our work with silver, no grain-size effect would be expected at temperatures above about 0.7 of the absolute melting temperature unless the grain size were exceedingly small. Likewise, in the investigation of the self diffusion of lead by Seith and Keil,14 the lowest temperature at which the diffusion coefficient was measured in polycrystalline specimens was 207°C, which is still sufficiently high so that the lack of a grain-size effect is not surprising. Finally, in those experiments on iron from which they concluded that there was no grain size effect, Drs. Birchenall and Mehl seem to have no information as to the actual grain sizes immediately prior to and following the diffusion anneal. Without this information, we believe that their own experiments offer little support for their hypothesis. F. S. Buffington, I. D. Bakalar, and M. Cohen—The results given in this paper agree in order of magnitude with those tentatively reported by us.27 However, significant differences exist in the two sets of data, and it may be well to make an explicit comparison. The diffusion studies at M.I.T. were conducted on somewhat higher purity iron (99.98 pct Fe) than the grades used by the authors, but this is undoubtedly not the answer. Fig. 4 shows the diffusion results of both laboratories for the gamma phase, omitting the authors' data on the commercial steels, while fig. 5 presents a similar comparison for the alpha phase. The divergence is much more marked in the latter case than in the former. In connection with the M.I.T. determinations, all of the runs in the gamma range and those above 800 °C in the alpha range were conducted with specimens having a relatively thick (0.002 cm) electrodeposit of radioactive iron. This practice minimizes any possible error due to extraneous diffusion that may occur during the heating to and cooling from the operating temperature. An exact solution of Fick's law for these boundary conditions was used in calculating the diffusion coefficients. At a later time, three runs were made below 800°C, using very thin electrodeposits similar to those of the authors, and the points fell considerably below the values expected from the extrapolation of the results based on the specimens with the thick deposits (compare dash-dot line in fig. 5). However, in the runs with the thin deposits, deviations of 100 pct were found between the individual specimens, whereas the maximum deviation with the thick deposits was less than 25 pct. Accordingly, it is not known at the moment whether the M.I.T. points below 800 °C should be given as much weight as those above 800°C. If this were done, the frequency factor would be of the order of 400 cm2 per sec, which is quite high. In other metals, the frequency factor for self diffusion lies between about 0.1 and 10 cm2 per sec. As the points below

Jan 1, 1951

By Peter R. Drummond

THE final casting of refined copper has been re-J- stricted for generations by the following sequence of operations: Filling the reverberatory furnace, melting, skimming, blowing or flapping, and poling. The hoped-for 24 hr cycle, producing 300 tons or more, has been taken up largely with the necessary bat time-consuming tasks of cleaning the bath, sulphur elimination, and in turn removal of excess oxygen to produce tough-pitch copper. Incidental to comparatively slow melting under combustion gases, copper oxides react with the furnace lining, and the slag so-formed must be completely recycled. The three-phase arc furnace has eliminated some of the cycle stages, and telescoped the remainder into a continuous operation. Electrical energy, supplied to graphite electrodes enclosed in high grade refractories, rapidly melts copper cathodes and sustains a stream of metal, containing approximately 0.01 pct oxygen, without contamination from fuel. The arc was struck on the first large electric furnace for melting copper in the United States on April 13, 1949. The earliest use of this type of furnace was at Copper Cliff, Ont., in 1936, and an admirable description of their installation has been published? Copper, melted in the Baltimore furnace, is used to cast billets, and the installation differs somewhat from the Canadian, as will be described. The arc furnace is a heavy-duty, three-phase furnace, holding 50 tons, the general outline of which appears on Fig. 1. The steel shell is 15 ft ID with a bottom radius of 14 ft 2 in. The roof, separate and distinct from the body, consists of a 15-ft water-cooled, cast-steel ring of the same outside diameter as the furnace. The center line of the furnace lies 9 ft 6 in. from that of the trunnions, permitting a 5" backward tilt for skimming, and a 40" maximum nose tilt forward for complete draining. Normally, the furnace overflows by displacement, and the use of the forward tilt arrangement is restricted to covering charging delays. The charging slot, 3 ft 8 in. x 5 in., lies on the north center line, the tap hole on the south, and the 30x30 in. skim door 45" to the west of the slot. The original 20-in. graphite electrodes were replaced with 14 in. in December 1949. Three conventional direct current winch drives, governed by electrical controls, position each electrode which has individual mast supports and counterweights. An independent circulation supplies cooling water for the electrode glands, the roof ring, charge slot, and the skim door frame. Arc Furnace Refractories Hearth: Fused-in monolithic bottoms had been used in copper arc furnaces, installed prior to April 1949. These consisted of thin layers of periclase, successively fused in place over preliminary brick courses. Heat was obtained from the arc, using a T-like arrangement of broken electrodes resting directly on the periclase to be fused. The operation, taking weeks to perform, was very expensive. The chemically-bonded magnesite-brick bottom, installed at Baltimore, was the first of its kind and a radical departure from previous practice. It consists of a 1 to 6-in. layer of castable refractory laid on the steel shell, modifying it to a 12 ft 2 in. bottom radius. Two courses of 9x2 % -in. fireclay straights and keys follow. The third course is made of 9-in. magnesite blocks of special shape to form circles of an inverted arch. It was started by a four piece keystone with skew-backs forming the outer course. The fourth course also started on a central keystone, or button, of four 90" segments, 12 in. diam x 13 Vz in. deep, and continued with 13%-in. blocks. Skewbacks at the shell completed the course to produce a horizontal surface for the side walls with a single course of No. 2 arch fireclay against the steel. Dry chrome-magnesite cement was brushed over each course after laying, and a 1-in. expansion space between the brick and the shell was filled with the same mixture. The total bottom thickness, excluding the castable material, was 5 in. of clay plus 22% in. of chemically-bonded magnesite. Tap Hole: A 5-in. OD and 3-in. ID silicon-carbide tube constitutes the tap hole and is set tangential to the upper course of the furnace bottom. Molten metal fills the tube when the furnace is level and filled to capacity. Side Walls: The lining, against the shell, consists of a 9x4Y2x3 in. soldier course of fireclay, using straights and No. 1 arches to turn the circles. A second soldier course of 9x4'/2x2'/2-in. fireclay was laid in a somewhat similar fashion. Three courses of 13Y2x6x3 in. and 9x6~3 in. of final magnesite, laid flat, completed the lining, using Nos. 1 and 2 keys to turn the circles. Cardboard spacers were placed between every two bricks in horizontal courses, and a thin coat of chrome-magnesite cement filled the joints between the firebrick and magnesite. A sprung-arch spanned the skim door with jambs of suitable magnesite shapes. Charge Slot: The slot is 3 ft 8 in. wide x 5 in. high. A silicon-carbide sill of special shapes has a 30" slope to allow cathodes to slide easily into the bath. The original arch was flat, and composed of Nos. 1 and 2 wedge magnesite with a 6-ft radius. It projected 5 in. over the sill, and, being a flat arch, gave an 18 15/16-in. opening between the inner edge and the metal line. The whole assembly was later raised 9 in., and the flat arch replaced with an arch, the lower edge of which maintained the 5-in, width from the outer to inner edges as shown in Fig. 2. A water-cooled, cast-copper jacket protects the steel shell behind the slot.

Jan 1, 1952

For the year ending February, 1919 PRESIDENT SIDNEY J. JENNINGS NEW YORK, N. Y. PAST PRESIDENTS L. D. RICKETTS NEW YORK, N. Y. PHILIP N. MOORE ST. Louis, Mo. FIRST VICE-PRESIDENT C. W. GOODALE BUTTE, MONT. TREASURER GEORGE D. BARRON NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 1, 1919

[Officers and Committees of the Society of Petroleum Engineers 1 Officers and Staff of the AIME 2 Officers of AIME Sections Predominantly Petroleum in Membership 3 Society of Petroleum Engineers By-Laws 5 Alphabetical List of Members 9 Geographical List of Members 110 List of Members by Companies 127 Advertisers' Index 137]

Jan 1, 1961

By Robert M. Jimeson, James M. Grout

The competitive market potential for solvent-refined coal is estimated and the market advantages are enumerated. Markets are possible in combustion, railroad locomotion, and carbon electrodes. The combustion characteristics are consistent with expected air pollution restrictions on the emission of sulfur and particulate matter. A market potential of sufficient size exists to support the initiation of solvent refining in the United States. The market analysis should help fuel producers determine the advisability of their undertaking solvent refining of coal.

Jan 1, 1972

By Elliot Rexford

The quality of aggregate materials is of major importance in governing durability and permanence of concrete structures. The problem of selecting suitable aggregate materials is two-fold. Geological factors include the type and character of the aggregate source, presence of known or suspected reactive constituents, and presence of thermally incompatible materials. Laboratory investigations include petrographic studies, soundness and reactivity tests, and tests of thermal properties. The importance of each factor in the selection of satisfactory aggregate material is considered in detail.

Jan 3, 1950

By J. H. Bechtold

Tensile properties of annealed molybdenum were investigated from 1000" to—200°C. In the vicinity of room temperature a well-defined transition in tensile properties occurs. Reduction in area decreases from over 80 pct to 0 pct and, simultaneously, the yield strength increases about 60,000 psi. MOLYBDENUM, tungsten, iron, and many other metals and alloys with the body-centered cubic and hexagonal close-packed crystal structures change from ductile to brittle behavior over some relatively narrow temperature range. The temperature at which this transition in ductility occurs depends on chemical composition, microstructure, and method of testing. When fine grained, completely recrystallized molybdenum of commercial purity is tested in uniaxial tension at a slow strain rate, the transition occurs at slightly below room temperature.' Iron2 and tungsten3 tested under similar conditions become brittle at temperatures close to the boiling point of nitrogen, — 195°C and at about 200°C, respectively. A sharp change in ductility is uncommon in metals with the face-centered cubic crystal structure, however, a relatively sharp transi- tion in notched bar impact properties has been observed below room temperature in a face-centered cubic copper-antimony alloy.4 A transition from ductile to brittle behavior is usually explained by the concepts originally developed by Ludwik,5 and discussed and elaborated on by others including Orowan,6 Hollomon and Jaffe,7 and Gensamer8 In brief, there are two aspects to strength, first the resistance to flow and second the resistance to fracture. Both are functions of temperature, strain, strain rate, stress system, composition, and microstructure. With decreased test temperature the flow stress required to initiate plastic deformation increases more rapidly than the fracture strength and brittle fracture occurs at that temperature where the yield strength equals or exceeds a brittle fracture strength. This investigation was conducted to determine the effects of temperature, strain, and rate of straining on the flow and fracture strengths of molybdenum above, through, and below the ductile-to-brittle transition. Other variables were held constant during testing. This information is believed to show

Jan 1, 1954

E. A. H. Tays, San Blas, Sinaloa, Mex. (communication to the Secretary*):—The results obtained by Messrs. Hofman and Hayward in their experiments, proving that a low percentage of copper sulphate with a variable percentage of salt, depending on the ore, gives the best results, confirm practical mill-work which I did in 1895. I have none of my notes, taken at the time, to refer to, so have to rely solely on memory, which precludes the conciseness that is alway desirable. In 1894 I took charge of the plant of the San Rafael Company, near Chinipas, Chihuahua, Mex., which at that time was treating a very refractory ore carrying about $15 in gold and from 20 to 25 oz. of silver per ton, the bullion being about 300 fine in gold. The silver in the ore was in the form of a sulphide. Although carrying an average of 0.75 oz. of gold per ton, free gold could rarely be seen by panning, but upon roasting a sample of the ore the gold became visible at once—a result which was discovered by chance and used to advantage later. In order to utilize the old mill to the best advantage, it was decided to use pan-amalgamation after roasting. The roasting, done in a lime-kiln, was similar to the ordinary " burning " operation. The roasted ore was trammed to the mill-bins and crushed by 10 stamps to pass a 30-mesh screen. The pulp was de-watered and fed to four 1-ton pans. My recollection is that upon starting the mill-work, the charge contained 1.5 lb. of copper sulphate and 5 per cent. of salt per ton. From the start the extraction was unsatisfactory and the loss of quicksilver was very large. Experiments were then carried out on a working scale. First, the quantity of copper sulphate was increased 4 oz. at a time; then it was reduced

Jan 1, 1910

By V. B. Kurfman

Grain refinement of Mg-Al melts by carbonaceous additions has been attributed to nucleation by aluminum carbide. The effects of process and alloy variables are interpreted and predicted in terms of the dispersion and chemistry of this phase. The grain coarsening action of Be, Zr, Ti, R.E., chlorination, temperature extremes, and prolonged holding times is described. Measures necessary to insure an adequate dispersion of the catalyst are discussed. CARBON inoculation treatments have become fairly well known and used for grain refinement of magnesium alloys containing Al. Although there is general agreement that a nucleation process occurs, the process is not understood and the inoculants are used in a rather empirical fashion. The treatment is applied to the class of alloys containing 3 to 10 pct Al, i.e., AZ31A to AM100A. Typical methods involve melting, alloying, and adjusting the temperature to 1400° to 1450°F. Then 0.01 to 0.5 pct C as CaC2, C6C16, or lampblack is added by any convenient means, and the melt poured within 10 to 30 min. Investigators generally have been impressed by an assumed similarity of this refinement process to superheat grain refinement, which depends on heating approximately the same alloys to a temperature in the range of 1550" to 1650°F, then pouring promptly after the melt is cooled to the pouring temperature. Various predictions have been made that carbon refinement would replace superheating in commercial practice due to reduced process costs, but this replacement has not fully taken place because of production difficulties and conflicting observations. Davis, Eastwood, and DeHaven1 agree with Nelson2 and wood3 in suggesting that an excess of inoculant may be harmful. Wood however says that overtreat-ment is not a problem in production use of hexa-chlorobenzene inoculation, and Hultgren and Mitchell4 claim no evidence of harm from excess additions. Various grain coarsening reactions are known to occur, including the possibility of overtreatment mentioned above. Trace amounts of Be,2 Zr, and Ti may prevent refinement by either a carbon treatment or a superheat. Occasionally treatment with cl25 may cause coarsening, although the Battelle refinement process' uses a CC14-C12 blend. Grain coarsening also tends to occur on holding at temperatures below 1350°to 1400°F, especially after a superheat treatment, and for this reason Nelson2 stresses the desirability of a refinement method useful at lower temperatures for open pot melting practice. Since a carbon treatment can be made to work at temperatures below 1400°F, it seems desirable to investigate the mechanism of the refinement and the mechanisms of the coarsening reactions in order to establish control conditions for use in commercial production. The identity of the nucleating phase must first be established and then the factors affecting its chemistry and physical dispersion must be determined. THE IDENTITY OF THE NUCLEATING PHASE Davis, Eastwood, and DeHaven suggested that the nucleating phase in this system is Al4c3,1 but Mahoney, Tarr, and LeGrand8 disagree, largely because they found no evidence of the compound in alloys after carbon treatment and because there is no indication that aluminum carbide should be unstable over the temperature range used in the superheat treatment. This latter objection is based on the assumption that both the carbon treatment and the superheat treatment introduce the same nuclei. Electron diffraction studies have been made to identify the nucleating phase. Samples of grain refined A292 have been selectively etched SO that clean surfaces are obtained and so that secondary phases are in relief. Electron diffraction patterns from these surfaces have established that the carbon treatment of A292 introduces into the metal a large number of small, plate-like particles with a structure very similar to Al4C3. In most cases, the plate-like nature of the particles prevented positive identification but in the cases where the identification could be made the particles proved to be AIN A14C3. However, enough variation in lattice constants was observed so that all compositions from pure A14C3 to the 50:50 solid solution A1N.Al4C3 were probably present.14 In A14C3 and especially AlN.Al4C3 the A1 atoms occur in layers within which they have the same hexagonal symmetry and spacing as the Mg atoms in a single basal plane of a magnesium crystal. The solid solution spacing lies between the 3.16 of AIN and the 3.3? for Al4C3, in satisfactory agree-

Jan 1, 1962

By Eduardo J. Chibas

Location.—The principal manganese-deposits of the Department of Panama, Republic of Colombia, are located almost clue south of Viento Frio, a native village bordering on the Caribbean Sea, and about 45 miles northeast of Colon (Aspinwall). The mining-claims are the Viento Frio, the Carrano, the Nispero, and the Soledad. Each property is to the south of the preceding one in the order mentioned. The first one is about one mile from the coast, and the most southerly boundary of the Soledad is about five miles in a straight line from the same coast-line. I shall confine my remarks to the four properties mentioned and to La Guaca, west of the Carrano, because these are the only ones where mining has so far been done to more or less extent. Manganese has also been found, however, in the neighborhood of these deposits, and a large area adjoining them has been divided into sections and " denounced " as mining-claims. The relative position of the manganese-deposits and Nombre de Dios, the present terminal of the railroad and shipping-port, as well as Viento Frio and the adjacent coast, can

Jan 1, 1898

By H. R. Ogden, E. S. Bartlett, A. G. Imgram

Unmodified disilicide coatirigs were applied to sheet-tensile specimens ofCb-Dg3 and Mo-TZM veJractovy- metal alloys. Coating thickness, degree of coating-substrate interdiffusion, and specimen geonzetry (notched and plain were included in the variables studied. Tensile tests were made to determine the ductile-lo-brittle transition temperature. The disilicide coating modestly increased the transition temperatlre of TZM, but had no effect on 043. Neither material condition (recrystallized or stress-velieved) nor specimen geometry (notched or unnotched) significantly altered the effects of coatings on the transilion temperatures of. the alloys. Cracks in the brittle coatings did not propagate into the substrate, and fracture modes appeared to be the same for both un-coated and coated specimens. MOST potential structural applications for refractory metals and alloys involve exposures to oxidizing environments at elevated temperatures. The general lack of oxidation resistance of these metals will require protective coatings to allow fulfillment of their potential. Currently preferred coatings for the oxidation protection of refractory metals are brittle intermetallic aluminides or silicides. These are typically formed on the surface of the refractory-metal substrate by a diffusion reaction between the substrate and a gaseous or liquid medium that is rich in aluminum or silicon. Because of the brittleness of these coatings, they will sustain no plastic deformation at low temperatures. They are frequently cracked by cooling from the coating temperature because of the thermal-expansion mismatch with the substrate alloy. Even if they survive cooling intact, they crack rather than sustain deformation under load at low temperatures. Thus, when a coated refractory metal is strained beyond the elastic limit of the coating at low temperatures, the mechanical environment of the substrate would include both static and dynamic cracks. These might be expected to influence the flow and fracture behavior of the substrate. This could be manifested in an altered fracture mode and/or an increase in the normal ductile-to-brittle transition temperature of the refractory-metal substrate. This paper presents the results of a research program that was conducted to determine the influence of the presence of a brittle surface coating on the low-strain-rate tensile behavior of typical refractory metals at low temperatures. EXPERIMENTAL PROCEDURES Material Preparation. Thirty-mil-thick sheets of molybdenum TZM alloy (Mo-0.5Ti-O.1Zr) and colum-bium D43 alloy (Cb-IOW-1Zr-O.1C) were obtained commercially. These alloys were selected as substrate materials representing two classes of materials important in current refractory-metal technology. The TZM was in the stress-relieved condition, and exhibited a heavily fibered grain structure. The D43 had been processed by the duPont "optimum" fabrication schedule,' and exhibited slightly elongated grains typical of this process. Tensile specimens of two geometries were prepared from these materials: 1) plain specimens with 0.2-in.-wide 1.0-in.-long gage sections; 2) specimens similar to above, but with a 0.06-in.-diam hole drilled in the center of the gage section, providing a stress concentration factor, Kt, of 2.5. The "notch" geometry was selected to represent a typical condition of a rivet hole or other geometric discontinuities as might be encountered in various applications. Machined specimens were degreased, with a final rinse in acetone, prior to the application of coatings. Specimens of each substrate and configuration were pack-siliconizedin a particulate mixture of 80 pct A1203, 17 pct Si, and 3 pct NaF. Specimens were embedded in this mix (contained in graphite retorts) and coated in an electrically heated argon-atmosphere furnace under time-temperature conditions to effect nominal 1- and 3-mil-thick silicide coatings: Coating Thickness, mils Thermal Treatment 0.6 to 1.4 24 hr at 982°C 2.4 to 3.2 48 hr at 1093°C Coating kinetics were similar for both the TZM and D43 substrates. These treatments had little or no visible effect on the substrate microstructure as determined by optical metallography. The coatings on TZM were essentially single-phase unmodified disilicides, while those on D43 showed substantial evidence of modification by proportionate reaction with the respective substrate elements or phases, as shown in Fig. 1. It was recognized that these coatings might not be particularly desirable regarding protective capability. However, it was desired to circumvent possible inter -ferring chemical interaction with the substrate by pack additives such as chromium, titanium, boron, aluminum, and other elements that typify the better protective coatings for these materials.' Thus, the results presented apply specifically to the simple silicide coatings investigated. They may not be rep-

Jan 1, 1967

By W. R. Hudspeth

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

Jan 1, 1952

By E. B. Fitch, E. C. Johnson

The operating behavior of liquid-solid cyclones is outlined, together with the nature and range of the process results obtainable, to serve as a background for engineers wishing to consider application of this new process tool. BY now most engineers are familiar with the liquid-solid or Dutch State Mines cyclone. However, it should be helpful to know exactly what it is that the equipment does and what its limits are. Without going into cyclone theory, this paper will describe the operating characteristics of Dutch State Mines cyclones. These are manufactured under license in this country and sold under the trade-marked name of DorrClone. The physical construction of the liquid-solid cyclone has been covered in many papers,'-' the DorrClone in particular being described in some detail by Weems. Fig. 1 shows the unit in cross-section. The feed enters at C. The coarse, heavy particles are thrown centrifugally to the periphery and make their way down the wall to the apex where their rate of discharge as underflow is controlled by an adjustable rubber apex valve. As the apex diameter is decreased the solids build up behind the valve, producing a denser underflow. Meanwhile the fine particles are swept into the upward flowing vortex stream which exits as overflow through the vortex finder, F. Flexibility to produce the specific result desired in a particular process is achieved by providing means for varying the areas of the entrance, vortex discharge, and apex discharge. The entrance area may be varied by insertion of special shims. Vortex discharge area may be changed by use of different-sized vortex finders which are interchangeable. Similarly, the different sizes of apex valves are interchangeable and in addition each apex valve is variable down to about 60 pct of its maximum diameter. A most significant primary distinction to make is that although liquid-solid cyclones have been sometimes called thickeners, they actually are classifiers, and very potent ones. They are almost never thickeners in the special sense that many metallurgical engineers understand the term. There would be no profit in quibbling over the definition of a word, but when the application of cyclones is considered, it will help to understand the difference be- tween two mechanisms, one of which will be called classification, and the other thickening. In what is called thickening the fine solid particles present in the feed hold together by surface attraction during the sedimentation process. The loose network of particles thus held together constrains all particles to settle at approximately the same rate, the larger ones dragging the smaller ones down. As a result, pulp settles with a sharp line of demarcation between solids and a relatively clear supernatant liquid. Essentially all the solids, regardless of their fineness, pass into the thickened underflow, and a clear overflow is separated. In classification, on the other hand, the interparti-cle forces are relatively insignificant as compared to the settling force on the individual particles, and are insufficient to prevent independent movement of the particles. The coarsest, heaviest particles settle most rapidly through the pulp, passing more slowly settling fines. Particles coarser than the mesh-of-separation essentially all settle into the underflow, but if the feed contains any particles finer than the mesh of separation, at least part of them will appear in the overflow. A clear supernatant or overflow can be obtained only if there are no undersize particles present in the feed. Thus it will be seen that classification is impossible under ideal thickening conditions. The finer particles are pulled down at essentially the same rate as coarser particles, and there is no separation on the basis of particle size. The surface attraction holding the particles together in a thickener is usually feeble. Whenever the sedimentation force on any particle is strong with respect to the interparticle forces, that particle can pass through the tenuous structure and settle independently. There are at least four ways of making the sedimentation force strong, with respect to the interparticle forces, and obtaining classification. First, and most obvious, the particles may be large and heavy. Thus coarse sands settle out in a beaker or Dorr thickener ahead of the rest of the thickening solids. Second, the interparticle forces may be altered by physicochemical means; i.e., it is often necessary to add dispersing agents to destroy the interparticle forces and permit classification to take place. Third, the interparticle forces may be reduced by dilution of pulp. It is well known that to obtain the most efficient separation of

Jan 1, 1954

By L. H. Van Vlack, T. Y. Tien, R. J. Martin

The phase relationships of the MnTe-MnS system were studied by DTA procedures. There is an eutectic at 810°C with about 10 mole pct MnS-90 mole pct MnTe. An eutectoid occurs at about 710°C with approximately 7 mole pct MnS where the MnTe(NaCl) solid solution dissociates on cooling to MnTe(NiAs) and MnS. There is very little solid solubility of MnTe in MnS. ALTHOUGH MnS may exist in three different crystal forms,' only the NaC1-type phase is stable.2 Above 1040°C, MnTe also has the cubic NaC1-type structure. Below that temperature, MnTe changes to the NiAs-type structure.3 This phase transition is rapid for both heating and cooling. As a result the high-temperature crystal form of MnTe cannot be retained at room temperature. Because MnO, MnS, and MnSe are all stable with the NaC1-type structure, and MnTe has this structure at high temperatures,4 solid solution formation could be expected among these compounds. It is interesting to note, however, that a complete series of solid solutions exist only in the MnS-MnSe system,' and that the solid solution is quite limited in the MnO-MnS system.' The MnSe-MnTe system possesses a complete series of solid solutions at high temperatures with separation at lower temperatures.7 Although ion size may be critical in the miscibility of MnO-MnS, it is quite possible that the bond type plays a more important role with the miscibility of MnSe-MnTe. This would permit us to speculate that the miscibility gap would be extensive in the MnTe-MnS system. EXPERIMENTAL Preparation. The samples were prepared by mixing and compacting MnTe and MnS powders. The MnS was previously prepared through the sulfur reduction of Mnso4.8 The MnTe had been prepared by mixing and compacting double vacuum distilled metallic manganese and high-purity tellurium in stoichiometric ratio modified with 1 wt pct excess tellurium. The compacted powders were put in a graphite crucible which was sealed in an evacuated vycor tube. The free space in the vycor tube was made minimal to reduce the loss of tellurium. The sealed assembly was then heated slowly to about 500° C where the free manganese and tellurium reacted vigorously, melting the MnTe which formed. Only one phase, MnTe, was detected by X-ray powder patterns and metallographic techniques. Each compact of MnTe-MnS was placed in a graphite crucible and then sealed in an evacuated vycor tube. The samples were heated at 1250°C for 4 hr and furnace-cooled. Microscopic examination revealed no third phase beyond MnS and MnTe. A typical microstructure is presented in Fig. 1. Identification. X-ray powder patterns were obtained using 114.6 mm Debye-Scherrer camera and Fe-Ka radiation. Mixtures of cubic MnS and hexagonal MnTe were observed in all of the compositions prepared. No lattice parameter change was noticed among different compositions, indicating no solid solution could be retained at room temperatures between these two end-members. A lattice parameter of 5.244Å for MnS was obtained by the Nelson and Riley9 extrapolation method using the diffraction lines of (h2 + k2 + 12) equal 12, 16, 20, and 24. The values, a = 4.145Å and c = 6.708Å, for hexagonal MnTe were obtained from the (006) and (220) lines in the back-reflection region. These values agree well with the values reported by Taylor and Kag1e.10 Differential Thermal Analysis. A differential thermal analysis procedure was used to determine phase relationships since the high-temperature equilibrium conditions could not be retained for examination at room temperature, even when the sealed samples (~0.5 g) were quenched in water. The samples were sealed in an evacuated 4 mm vycor tube with a recess in the bottom to accept a thermocouple. An Al2O3 reference was similarly prepared and the two placed within a piece of insulating fire brick to dampen spurious temperature changes within the furnace. The furnace was controlled by a mechanically driven rheostat which increased the temperature at a rate of about 15°C per min. Known phase changes in the Pb-Sn system1' and the a-to-ß quartz inversion12 were used for calibration

Jan 1, 1969

By J. Winlock

To have been chosen by you to give the Howe Memorial Lecture is the greatest honor I have ever had and I should like to have you know that I appreciate it deeply. Many years ago I had the privilege and the pleasure of working with Professor Howe in the private laboratory which he had established in his home at Bedford Hills, New York. Without doubt he was one of the world's greatest metallurgists and so you can imagine what a difficult task it has been for me to live up to his teachings. Every morning Professor Howe would outline the work he wanted done and the recollections of those conferences are clear to me to this day. Sometimes he would ask me to ride in his automobile and the chauffeur had full instructions to go no more than fifteen miles an hour. If he did so, Professor Howe was sure to rap upon the man's shoulder with his cane. I assure you, however, Professor Howe's thinking was not at that rate. His homely advice, his patience and his perfect control of the English language still impress me. Many times I heard him dictate a complicated paper on metallurgy and never find it necessary to change a single word. There are no better words to describe the character of Professor Howe, in my opinion, than those used by Professor Sauveur when he presented the John Fritz Medal to him in 1917: "Lover of justice and humanity Public servant and public benefactor, Master of the English Language, Loyal and devoted friend, Untiring and unselfish worker in an important field of science." I hope you will bear with me with the same patience and understanding which he used to give to me. The peculiar behavior of steel at the yield point has long been known and has been the subject of much research, both in this country and abroad.',' Many theories, including some of mine and my colleagues, have been suggested, but none of them, in our opinion, fully explains to our satisfaction why the phenomena occur. Of particular importance has been the work of Nadai,3 Siebel and Pomp,' Sachs and Fiek,5 Rawdon,0 Kenyon and Burns,' Gensamer," Gensamer and Meh1,0 Davenport and Bain,'" Fell," Deutler,12 Brinkman,13 MacGregor,14 Hollomon,15 Cot-trell,16 and Palm." The question of what is occurring during this singular behavior is not only of interest from an academic point of view, but is of great practical importance for at least two reasons: 1—The highly localized plastic flow which occurs during the deep drawing of light-gage steel gives rise to surface markings which seriously mar its appearance, Fig. 1. If the forces causing the deformation are primarily tensile forces, these surface markings occur as depressions in the surface. Whereas, if the forces causing the deformation are primarily compressive, irregular lines of elevations occur. These surface markings are known as Luder's lines, Hartmann lines, the Piobert affect, and, in the shop, as "stretcher strains." 2—The steel is in the most suitable condition for deep drawing after the yield point phenomena have been removed. When this is done, the steel may be deep drawn more easily and to a greater extent.' It should be mentioned that steel is not the only metal which shows this peculiar behavior at the yield point. Stretcher strains occur, also, during the deformation of some copper-nickel-zinc alloys." The purpose of this paper is not an attempt to describe what causes the steel to behave in this peculiar manner, but an attempt: l—to describe what is taking place at the yield point; and 2—to show the influence of the rate of deformation on the tensile properties of some plain carbon steels. As is well-known, there are two methods of deforming a metal in tension: 1—by actually hanging an increasing amount of dead weight on the metal; or 2—by deforming the metal at some given rate or rates by means of oil pressure cylinders, screws, etc. With the first method, the load is always present and, clearly, no drop in load can ever occur while the steel is deforming. With the second method, the registered load is the resistance of the steel to the deformation being imposed upon it. The second method is the one most widely used, and is the one referred to throughout this paper. In order to describe clearly what is occurring at the yield point in steel, it will help, I believe, if a description is first given of what occurs when alumi-

Jan 1, 1954

By John C. Gifford, Charles L. Thomas

A unique and reproducible method is presented for the determination of water vapor in tough pitch wire bar copper. The procedure involves reduction of the water vapor with molten aluminum to form hydrogen, which is subsequently measured by mass spectroscopy. Average water vapor pressures within the porosities of the wire bar samples are calculated. Correlation is to exist between the specific gravities of the samples and their measured water vapor contents. The method should find application as a very sensitive means of detecting hydrogen embrittlement in copper. The nature and quantity of gases evolved and retained during the horizontal casting of tough pitch wire bar copper have long been of interest to the metallurgist. Considerable work has been done at this laboratory on the determination of these gases. The work has involved not only qualitative but also quantitative analysis, so as to provide a basis for a total accounting of the porosity which is associated with the cast product. From a knowledge of the gas-forming elements within the copper, and the practice of melting and protecting it with a reducing flame followed by contact with a charcoal cover in the casting ladle, the gases which one might expect to find in the pores of the cast product are sulfur dioxide, carbon monoxide, carbon dioxide, hydrogen, and water vapor. Hydrogen sulfide, nitrogen, and hydrocarbons would be other possibilities; however vacuum fusion-mass spectroscopy techniques employed at this laboratory have shown that no hydrogen sulfide and only traces of nitrogen and methane are present. It is highly improbable according to phillipsl that any sulfur dioxide could be evolved in wire bar copper with 10 ppm or less sulfur under normal freezing conditions. Mackay and smith2 have noted that porosity due to sulfur dioxide only becomes noticeable at concentrations above 20 ppm S. Investigation of carbon monoxide and carbon dioxide by a variation in the method of Bever and Floe showed that these two gases could only account, at 760 mm and 1064°C (Cu-Cua eutectic temperature), for a maximum of about 25 pct of the total porosity in a wire bar having a specific gravity of 8.40 g per cu cm. phillips' has noted that no normal furnace atmosphere is ever sufficiently rich in hydrogen to cause porosity in copper from hydrogen alone. In addition, using a hot vacuum extraction technique for hydrogen,4 values have never been observed in excess of 10 ppb in tough pitch wire bar. On the basis of the preceding considerations of gases in tough pitch wire bar, only water vapor is left to account for the major portion of the porosity. Direct determinations of water vapor are virtually impossible at low concentrations by any presently known technique, due to adsorption and desorption within the walls of the apparatus used.5 The present investigation deals with a method for the determination of water vapor by an indirect procedure, using molten aluminum as a reducing agent to form hydrogen according to the reaction: 2A1 + 3H2O — A12O3 + 3H2 The evolved hydrogen can then be measured quantitatively by mass spectroscopy. EXPERIMENTAL A 10-g piece of 99.9+ pct A1 was charged into a porous alumina crucible (Laboratory Equipment Co., No. 528-30). Fig. 1 shows the crucible in place at the bottom of an 8-in.-long quartz thimble. A funnel tube with two l1/8-in.-OD sidearms extending at a 90-deg angle from each other was attached to the top of the thimble. One of the sidearms was joined to the inlet system of the mass spectrometer (Consolidated Electrodynamics Corp. Model 21-620A) via a mercury diffusion pump situated between two dry-ice traps. The copper samples were placed in the other sidearm, followed by a glass-enclosed magnetic stirring bar for pushing the samples into the crucible. All ground joints were sealed with vacuum-grade wax. The entire system was evacuated and the aluminum was heated with a T-2.5 Lepel High Frequency Induction Furnace for 21/2 hr at a temperature visually estimated to be 900°C. The temperature was then lowered and the hydrogen was monitored on the mass spectrometer until it was given off at a constant rate of about 4 to 5 1 per hr. This rate corresponded to a slope of 2 to 3 divisions per min on the X3 attenuation of a 10-mv recorder at a hydrogen sensitivity of approximately 100 divisions per 1. A micromanometer (Consolidated Electrodynamics Corp. Model 23-105)

Jan 1, 1969

By Y. Nakada, U. F. Kocks, B. Chalrners

THE orientation dependence of work hardening has previously been studied over the entire range, i.e., including special orientations of high symmetry, in aluminum1-3 and silver.* The differences between various orientations are substantial, and the trend is the same in all fcc crystals. However, there are quantitative differences in behavior between aluminum and silver at room temperature, particularly in the (100) orientation. While many experiments on gold have been reported,5'9 none included the special orientations. We therefore undertook tension tests on gold crystals of the axial orientations (100),(110), (Ill), (211), and, as a representative of single slip, one whose Schmid factor was 0.5 (hereafter referred to as m = 0.5). Single crystals of dimensions 1/4 by .1/4 by 6 in. were grown from the melt1' at a rate of 4 in. per hr, using gold of 99.99 pct purity obtained from Handy and Harman. A growth rate of 1/8 in. per hr, or a purity of 99.999 pct,ll produced no difference in results. The crystals were annealed at 1000°C in air for 24 hr and furnace-cooled down to room temperature, after which they were electro-polished in a solution of potassium cyanide (40 g), potassium ferrocyanide (10 g), soda (20 g), and enough distilled water to make 1 liter of solution, at a current density of 0.02 amp per sq mm. After 2 or 3 hr, a very smooth surface was obtained by this method. Nine m = 0.5, two (loo), one (110), three (Ill), and one (211; crystals were tested at room temperature in a floor-model Instron machine at a tensile strain rate of 0.5 pct per min. The accuracy of the stress measurement was k10 g per sq mm up to 500 g per sq mm, k2 pct for higher stresses. The strain measurement was accurate to t2 pct. The scatter of stress at a given strain among the crystals of the same orientation was small, *5 pct being the largest. The representative stress-strain curves for various orientations are shown in Fig. 1. Table I summarizes the work-hardening parameters as used by seeger.12 Results of other investigators are also included in this table for comparison. There are no previous data for the corner orientations. Values for m = 0.5 crystals agree fairly well with those of Berner. Tm is defined as the stress at which the stress-strain curve begins to deviate from linearity of Stage 11. However, in practice this is a very difficult value to estimate because each investigator has a different idea of linearity. Therefore, the comparison with the values of other investigators may not be valid. In the present experiment, (100) crystals had the highest 111, followed by (111) crystals. The work-hardening rate in Stage I1 was highest for the (111) crystal followed by the (100) crystals. Our value for 0x1 of m = 0.5 orientation agrees very well with those of other investigators. 1) Single-Slip orientation (m = 0.5). These crystals were oriented so that the primary-slip vector was contained in one side face. The dimension perpendicular to this side should then not change if single slip indeed takes place. Within the accuracy of measurement, this dimension did not change during the deformation. Since the accuracy is k0.2 pct, the amount of secondary slip is less than 0.7 pct of the slip on the primary-slip system at 30 pct tensile strain. This is in conformity with the results obtained by Kocks" for aluminum crystals. The tensile axis moved toward (211) during the deformation. Slip bands, Fig. 2(a), were very fine and closely spaced. Some deformation bands were observed. There were no clear-cut cross-slip traces such as the ones observed on aluminum m = 0.5 crystals. 2) (111) Crystals. The orientation of the tensile axis was stable during the deformation. From this observation, one can deduce that at least three slip systems must have operated, and probably all six because the remaining three all have cross-slip relation to one of the first three.' It was very difficult to observe the slip markings. Consequently, we could not confirm by this method that six systems were operative during the deformation. At high strains (above 50 pct shear strain), this orientation had the highest stress-strain curve. At 80

Jan 1, 1964

By P. Greenfield, C. C. Smith, A. M. Taylor

J. E. Harris (Berkeley Nucclear Laboratories, England)—Greenfield et al.11 attribute abrupt changes in slope of their log o/log i curves for heat-treated Mg/0.5 pet Zr alloy (zA) to &apos;atmosphere&apos; locking. It is proposed here that a more reasonable explanation of the apparent strengthening at low rates of strain can be based on precipitation either during the preanneal or during the creep tests. All the tests were carried out above 0.5 Tm where solute atmospheres are likely to be largely evaporated2 and can migrate sufficiently rapidly so as not to impose any &apos;drag&apos; on the moving dislocations. McLean3 has derived an expression for determining the temperature Tc above which, due to the high-migration rate of the atmospheres, Cottrell or Suzuki locking can play no part in determining creep strength. This expression, which holds for an applied shear stress of not greater than 5 X 107 dynes per sq cm is: Tc/Tm= 7/6.8 - log10? where i = secondary creep rate The values for T, corresponding to the maximum and minimum reported creep rates at each temperature have been calculated from the data of Greenfield et al. These are given in Table VII. All the test temperatures were above T,, the margin being greater for the higher temperatures and for the lower strain rates where the breaks in the log s/log ? curves occurred. Dorn and his collaborators14, 17 have studied systematically the effect of solute hardening on the creep properties of an A1/3.2 at. pet Mg alloy. In the temperature range where strain aging occurred in tensile tests, abnormally high-activation energies for secondary creep were obtained but at temperatures above 0.43 Tm, solute alloying did not have any effect on the creep parameters. Moreover, there have been no reports of any strain aging phenomenon during elevated temperature tensile tests with ZA material.18 Instead of the observed strengthening being due to atmosphere locking, it is now proposed that precipitates play an important role in enhancing the creep strength of the material. There are two possibilities—precipitation of zirconium hydride during the high-temperature preanneal and/or precipitation of the hydride or a-zirconium during creep. On the basis of the former the results can be interpreted in terms of a critical stress being necessary to force the dislocations through or over preexisting precipitates. From the latter, if the strengthening is due to pre- cipitation during the test then hardening should be associated with a critical strain rate. At low rates of strain, time is available during the tests for precipitation to occur either directly onto dislocations (thus pinning them) or generally throughout the matrix (which would impede dislocation movements). Examination of the data of Greenfield et al. suggests that both mechanisms may be operative since they observed precipitation during creep and also found that their alloys exhibited high-creep strength in the early stages of the low-stress tests, i.e., before creep-induced precipitation had time to occur. It is not easy to understand why they considered that precipitation of zirconium hydride is unlikely to occur at 600°C while it can take place in tests in air at as low a temperature as 200°C. Precipitation of the hydride during the preanneal cannot be ruled out merely on the basis of metallographic examination. Hydride precipitates in ZA type alloys are very small and can only be accurately resolved in the electron microscope.9 For example, in this laboratory20 hydride platelets with major dimensions <(1/10) µ have been observed by electron transmission through thin film specimens of hy-drogenated ZA material. Complex interactions between dislocations and such particles are illustrated in Fig. 12. Additional evidence for precipitation during pre-annealing is provided by the data presented in Greenfield&apos;s Fig. 1 and Table IT. These show that the creep strength at 200o and 400°C increases with the time of preanneal at 600°C. Such increases cannot be explained on the basis of increases in grain size alone for further improvements in strength were observed when the material was annealed for longer times than that required to stabilize the grains. Although the main discussion is confined to ZA material, similar arguments can be used against the strain aging hypothesis proposed to explain the binary Mg/Mn alloy data. In this case no precipitation is possible during the preanneal, but precipitation-hardening during creep can occur.

Jan 1, 1962

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 J. C. Martin

A theoretical analysis of steam stimulation is presented for single sands. The analysis includes the effect of steam production and most of the effects of heat conduction. The results show the effects of a number of important variables on the performance of an idealized well under steam stimulation. Calculated responses are presented which indicate the effects of steam production, amount of steam injected, water production, formation thickness and formation damage. Results indicate that steam production can cause large reductions in the heat contained in the formation. This effect can be eliminated by drawdown control. Water production reduces the amount of oil produced during stimulation. The optimum amount of steam to inject depends on economic factors as well as the well response. In many cases, the increased temperature resulting from stimulation reduces oil viscosity near the well sufficiently to overcome the effects of formation damage even if the damage is not removed during steam injection. Calculated responses for thin sands are more favorable than anticipated. INTRODUCTION Little has been published on the theory of steam stimulation&apos;-&apos; despite the interest it has created and the wide variation in well responses. The results of the present analysis provide an insight into steam stimulation, and the methods employed provide a foundation for future work. Analyses presented in Refs. 1 and 2 are very limited and apply to gravity drainage conditions. Ref. 3 contains an analysis similar to the one presented here. The idealized models used and the assumptions made in Ref. 3 are different from those used in this paper. The analysis assumes that after steam injection has heated a small portion of the volume within the radius of drainage of a single uniform sand, a shut-in soaking period is allowed before returning the well to production. The effects of gravity, capillarity, transient pressure and water-sensitive sands are neglected. The injection and soaking times are assumed short compared to the stimulated production time. The initial temperature is assumed uniform; thus, the results apply primarily to first-cycle stimulation. The effects of gas production other than steam are neglected, and the water-oil ratio during production is assumed constant. Steam stimulation involves the simultaneous variation of the temperature, pressure and saturations. General mathematical equations for these variations are complicated and can be very difficult to solve. Simplified equations based on idealized models are used to reduce the mathematics sufficiently to allow approximate solutions to be obtained. DISCUSSION INJECTION An idealized model for which heat conduction is neglected is used to represent the behavior of a well during steam injection. The mathematics for this model is presented in Appendix A which also contains an approximate solution for the behavior of the no-conduction model. SOAKING During soaking, the well is shut in. Only the temperature, pressure and saturation distributions at the end of soaking are needed in the analysis. During soaking the heat is considered to be conducted in a uniform medium from an initially uniformly-heated circular cylinder confined to the producing interval. At the end of soaking the saturations and pressures are assumed to correspond to the cold zone. Analysis of the heat flow during soaking is included in the next section. The radius of the heated cylinder is calculated from the following heat balance (for constant quality steam injection). At the end of the soaking period it is assumed that little or no free gas is present near the well, and that the soaking period has been sufficiently long that the steam zone has had time to expand and the steam has condensed. The condition where there is no soaking is considered in the next section. PRODUCTION In this section, an approximate method is presented for solving the equations of heat and fluid flow associated with the production of oil and water during steam stimulation. Where initial pressure drawdowns are sufficient to cause steam to flow into the wellbore, steam production is assumed to occur within a short initial adjustment period (Appendix B). The production practices followed soon after the well is returned to production can have a large influence on the amount of oil produced during the stimulation cycle. Under most conditions, there is a period of time in which some or all of the water in the heated zone is converted into steam and produced. This flashing of hot water is caused by the pressure in the heated zone dropping below