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By Albert R. Ledoux

Discussion of the Paper of Albert R. Ledoux, read at the Atlantic City Meeting, February, 1904. ARTHUR JARMAN, Sydney, New South Wales, Australia' (communication to the Secretary*): Some remarks upon. Dr. Ledoux's interesting paper from one who has not visited America may, I hope, be of interest to members. It appears to me that there is considerable difference between the training of the American and of the British mining engineer. Not that the subjects are different, but rather in the way in which they are handled, the illustrations being, as far as possible, mining in character. Colloquial instruction is unknown in English curricula, but could be introduced with advantage. Students here assure me that an hour of conversation is of tar more use to them than an hour of the best lecturing. In England a school-year of 6 or 7 months would be considered very short indeed; but Americans do not consider it so, for the reason that the rest of the year is mostly spent in acquiring practical acquaintance with their subjects in works or in the field, and the shorter courses, when coupled with this large amount of outside expe¬rience, produce an essentially practical-minded engineer, who is also more of a business man; whereas the English system, though excellent from a scholastic point of view, produces the theoretical rather than the practical man. British schools are waking up, however, and the practical aspect of the engineer's training is receiving greater consideration. Once launched upon his career, the American engineer is immediately called upon to exercise his self-reliance and ingenuity, if he is to retain the confidence of his employers; but what can we say of English directors? In how many cases is the engineer allowed to guide the destinies of his company? Witness several recent cases of gross waste of money upon unsuitable plants, and the perpetuation of prehistoric methods of

Mar 1, 1905

By A. T. Schwennesen

(Wilkes-Barre Meeting, June, 1911.) EVERY engineer has occasion to trace or copy a map, plan, or other drawing on paper too thick for the ordinary way of using tracing-cloth or tracing-paper. When the figure is small and simple a copy may be made by holding the original against a window-pane, covering it with the paper, and tracing direct by the aid of the strong sunlight from outside. The need of utilizing this principle on a larger scale and in a more convenient position led Dr. J. C. Branner to plan the table of which the following is a description: This table was first made in the form of an adjustable glass-top table with a mirror beneath, in 1887, while Dr. Branner was State Geologist of Arkansas. Later it was modified as experience suggested until the form as here described was evolved. The device consists essentially of a drafting-table with a plate-glass top, upon which the original drawing and the paper are laid, and a mirror mounted underneath to reflect the light of the sky up through the drawing. The glass top is hinged and fitted with two arms and thumb-screws, so that it can be raised and fixed to any position, either inclined or horizontal. The mirror is pivoted and revolves about a horizontal axis, so that it may be tilted to any angle. The hood of cardboard or black cloth prevents the reflection of light from the tracing, and may or may not be attached to the table. The apparatus is set up before a window through which part of the unobstructed sky is visible. The mirror is then adjusted like the reflector of a microscope, so that the skylight is reflected up through the drawing. If the mirror can be so located that the direct rays of the sun are reflected through the drawings, thicker paper can be used. The map or drawing may be held in place by clips screwed

May 1, 1911

By E. B. Viljoen

I. R. M. Chaston* As a gravity concentration man in the midst of so many eminent flotation experts I feel like Daniel. However, I would respectifully disagree with the opening remarks by Mr Viljoen. First, he suggested that gravity concentration of cassiterite was not effective in sizes below 30 microns. In a paper to the Institution of Mining and Metallurgy in 19621, I gave some figures for gravity concentration of deslimed material both for cassiterite and for wolfram which indicated that careful shaking table concentration of fine deslimed material could give recoveries of 75 to 90 percent in the size ranges above 13 micron. These were figures obtained from normal plant operation. It would be interesting to know if any tests were carried out on gravity concentration of the efficiently deslimed feed to this flotation plant to see what the recovery would be. Secondly, Mr Viljoen suggested that gravity concentration plants were expensive. He gives the cost of a flotation plant at R300 000 to treat a feed of 400 t.p.d. to the desliming section or 160 t.p.d. to the flotation cells. From his operating cost figures it would appear that the flotation cost is approximately R2 to R4 per ton of feed to flotation and the total operating cost about R2 per ton of feed. A table plant to treat this tonnage of deslimed feed would consist of about 30 tables and should cost considerably less to install and very much less to operate than the flotation plant. Third, Mr. Viljoen suggests that the concentrate grade from a gravity concentration operation would be unacceptably low. The paper quoted abovel showed that once a primary fine concentrate had been made, giving a suitably deslimed material, further gravity concentration could give concentrates of over 40 per cent Sn with high recoveries. Tailing from this dressing stage was naturally returned to the feed. To give these high grades, sulphides had been removed by flotation but this necessary flotation step is simple and cheap to operate and could be restricted to the final stage when the quantities involved are small. I would agree that flotation has a part to play in fine tin recovery but this role would only seem to become fully effective at sizes below 10 micron and would seem to require, as Mr. Viljoen has suggested, a mechanism for sizing which is effective down to, say, 1 micron. In the meantime it would be interesting to try tabling the flotation tailing to see if it was possible to recover the plus 20 micron cassiterite which is not recovered well by flotation. One point which has been made during discussion is the suggestion that cassiterite particles have a fully hydrated surface at normal pH. I wonder if this layer could materially affect the overall specific gravity of a very small cassiterite particle and, if so, whether gravity concentration of the very fine cassiterite would be improved if carried out in acid conditions, which would inhibit the formation of this hydrated surface. REFERENCES 1. CHASTON, I. R. M. 'Gravity concentration of fine cassiterite'. Trans. Inst. Min. and Met. Vol. 71, p. 4, 1961 and 1962, and discussion of this paper. Dr. R. P. King Mr Viljoen has drawn attention to the difficulties associated with the presence of very fine particles in the flotation pulp and he has indicated that, on the Union Tin plant, they must sacrifice 30 percent of the cassiterite in the minus 7 /Lm material which they separate and lose. He has also indicated that the rate of flotation of cassiterite remained high at these small sizes. The problem arises because the very small particles stabilize the froth making it impossible to handle. These stable froths cannot be easily broken and therefore cannot be pumped and processed. It seems that further fundamental research work on the properties of stabilized froths is urgently required. We have found another difficulty associated with the presence of very fine particles in phoscorite slurries; these particles can be easily floated but with very poor selectivity. We believe that it is possible that a purely physical mechanism such as entrainment is responsible for the collection of fine particles in the froth. We have also demonstrated that the presence of fine particles in the pulp adversely affects the rate of flotation of the larger particles. For esample, we have found an increase in recovery of + 100 um material from 2 percent to 17 percent in a standard laboratory batch flotation test on phoscorite when the - 37 um was removed from the feed. Such interactions between particles are not universally recognised as an important aspect of the complex flotation mechanism. They should appear in any quantitative formulation of the flotation rate process.

By Leonard H. Goldman, Harold E. Marr

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

Jan 1, 1980

By H. Lyn Bourne

This is the sixth annual tabulation that gives mineral royalty information. This tabulation, like the previous editions, includes all of the earlier data plus more than 100 new entries. In addition to the royalty information, some entries show the cost of purchased reserves. An article in the December 1984 Kentucky Coal Journal could have far reaching applications. It explains that a banking firm examined the "reserve risk" as one of six factors for analysis when financing a coal project. The firm concluded that coal reserves in Kentucky are worth an average of $0.29/t ($0.26 per st) in-place. The banking firm based this in-place value on its examination of more than 50 leases. In-place value is especially important when trying to establish a mineral value for a given deposit. Ernie Lehman wrote to this author after last year's column appeared and he quoted the lease rates for lead and zinc on federal land. He states, from first hand information, that the leases are based on a percentage of net smelter return as follows: 4% for the first five years, 4.5% for the next five years, and 5% thereafter. The figures used in last year's column ($ per st) came from dividing reported royalty income by reported production. The information reported last year merely translates the results of the net smelter return (as written in the lease) to royalty income per ton to the US Government for the various years. Statistics from the Minerals Management Service of the Federal Government show that oil and gas account for 40% and 53%, respectively, of the Federal royalty income. Coal accounts for about 4% and all other minerals, the remaining 3%. Oil and gas leases are mostly at 12.5%. Most of the coal leases are at 12.5% for surface mining operations and 8% for underground mining. Many of the other commodities are leased at 5%, which has been true for decades. Relative to Federal leases, this year's table shows some percentages and some costs per ton. This was done to give information about the leases and also to show income produced by various commodities. Note that some commodities have a variation in $/ton even though the royalty percent is the same. These variations result from a combination of factors that influence the value of a mineral commodity. The same caveats that have appeared in previous columns relative to factors that influence the value of reserves are restated. The data in the table serve as a general reference and are not intended to present an absolute scale of reserves costs. Several factors influence the value of any mineral commodity. The factors include: • location/transportation (especially significant for most industrial minerals); • market conditions both for the commodity and the company acquiring the right to mine it; *quality or grade of the deposit as it reflects the amount of processing/beneficiation necessary to produce the finished product; and • legislative restrictions and conditions for mining a given material at a given site. These and other factors will significantly influence the cost of reserves. The table shows the range of royalties and the variations in the basis of computing the fees. In a few instances, it gives the cost of acquired reserves based on purchase price and quantitative estimates of the material in place. The table lists the commodity in column 1, and the subsequent columns give the location - either by state, US geographic area or Canadian province; the cost - R for royalty and P for purchased cost; and the year in which the lease or purchase agreement occurred. The last column offers either comments or gives a footnote number for more information. The cost column requires more explanation. The units may refer to cubic yards (/yd), cubic feet (/cu ft), tons (/T, 2000 lbs) or acres (/A). 1 cu yd = 0.7646 m3 1 cu ft = 0.2832 m3 1st=0.9078t 1 acre = 0.4047 hm or m2 In several cases, the royalty is a percentage of the sales price of the finished product and is levied against either the amount produced or the amount sold. We thank those who contributed information for the table: G. Anderson, B. Brown, R. Ganis, K. Hauser, E. Lehman, and S. Sims. Their help is appreciated as are the contributions by those who asked to remain anonymous. This column requires additional information each year. That data must come from people in the minerals industry who have royalty information. What appears in the table is only a very small fraction of the cost information relative to the various commodities and the geographic areas for which there is royalty information. If you find this column of interest and possess information write the author at the address given in the author's box or call 313-462-0005.

Jan 7, 1988

By G. H. Anderson

H. R. HANLEY*—I have been asked to discuss briefly the development of rotating cathodes for the electrolytic deposition of cadmium. The earliest recorded use of rotating cathodes was by Hoepfner at Frufurt, Germany about sixty years ago. He elec-trolized zinc chloride solution using diaphragms to separate electrodes. In the early experimental work of the Bully Hill Copper Mining and Smelting Co., Shasta County, Calif., rotating aluminum cathodes 4 ft in diam were used in the electrolysis of an acid zinc sulphate solution. Finished cathodes weighing up to 400 lb were produced. Because of mechanical difficulties, this type of cathode was abandoned for zinc, but was later used for cadmium because of the relative smoothness of deposit in comparison with stationary plates with comparable current densities. Cadmium sponge which forms on the cathode at moderate current densities (without special treatment) is entirely eliminated by a slow rotation. The rate of rotation of the cathode has an effect on the mechanical nature of the deposit. A high rate of rotation concentrates the adhering electrolyte on the shaft; a moderate rate appears to concentrate on the cathode a short distance out from the shaft tending to corrode the deposit in the form of a ring. At a very slow rotation (2 to 3 rpm) the adhering electrolyte gravitates nearly vertically, thus avoiding the cutting ring referred to above. The true explanation for the smoother deposits obtained on rotating cathodes may not be given definitely as the numerous factors involved are not thoroughly understood. Smooth deposits are obtained when the orderly growth of the metal crystals in the cathode lattice are disorganized. Thus the crystals form and grow for a very short interval when they are arrested and a new crystal forms. The continued growth of the original crystals provides large crystals and a rough deposit. Also if the acidity of the electrolyte is low, hydrogen gas bubbles adhere to the deposit. As the cathode is rotated the gas surface is brought into the atmosphere where they burst; thus the deposit is made on a surface relatively gas-free. An aluminum hub distance piece was riveted to each aluminum disk 4 ft in diam, slipped on a 4 1/2 in. steel shaft and pressed tight to prevent acid electrolyte seeping through to the shaft. The 9-cathode assembly was supported on insulated bearings. Electrical contact to the shaft was made through what was equivalent to a copper pulley. Sufficiently high conductivity brushes were placed on the face of the pulley to lead the current to the cathode bus bar. The assembly was driven by a link belt contacting a sprocket insulated from the shaft. The lead anodes were semicircular and supported on porcelain insulators placed on the bottom of the cell. Two anodes were provided for each cathode to permit an 8-in. space between them without increasing the ohmic resistance. This ample spacing permitted easy stripping of deposit with the assembly in place. Cathode cadmium was melted under 650 W cylinder oil. After casting, the primary slabs were remelted under molten caustic soda and cast into pencils 1 1/32 in. in diam. Rotating cathodes for deposition of cadmium are used at Risdon, Tasmania, and at Magdeburg, Germany. W. G. WOOLF*—This paper is very-interesting to me because in our work at the Electrolytic Zinc Plant of the Sullivan Mining Co. we had an exactly similar problem—that is, a method of producing cadmium from our purification residue, the recovery of the contained copper as a copper precipitate which could be sent to a copper smelter and the production of merchantable cadmium. It is interesting to me, not knowing of the work of the Risdon people, how closely we approximate them in their main metallurgy, diverging at several interesting steps which I would like to discuss for just a moment. For example, at Risdon they oxidize their purification residue. In our practice we take the current residue as it is produced in the purification department of the zinc plant and process it in the cadmium plant. The only oxidation that it obtains is the oxidation in the presses, the dumping of the presses and the collection and transportation of the residue to the cadmium plant. We find that the leaching of that residue does not necessarily require the oxidation step that the Risdon people evidently find necessary. The discussion of oxidation comes in again in the matter of the treatment of the precipitated cadmium sponge with zinc dust which again at Risdon is oxidized but which we do not attempt to oxidize except as it oxidizes itself in the storage. There is a partial oxidation which cannot be avoided, as Mr. David-sou pointed out, but we make no attempt to attain a complete oxidation and we dissolve the cadmium sponge in the sul-

Jan 1, 1950

By Stanley L. Lopata, Eric B. Kula

SEVERAL methods are available for determining pole figures by X-ray means.' The earlier film methods have been replaced by techniques in which the intensities are measured by Geiger counters on an X-ray diffractometerZm7. These methods utilize either flat transmission or reflection samples,214°8 cylindrical specimens,3 or spherical specimens.7 A single transmission or reflection sample will not yield information over the complete pole figure. The cylindrical specimens suggested by Nortod and the spherical specimen of Jetter and Borie7 have the advantage of allowing the whole pole figure to be obtained without any corrections to the intensity for absorption, There is a lower limit to the size of sheet which can be conveniently studied, however, and sample preparation can be rather tedious. Probably the most common method today for determining the complete pole figure is that developed by Schulz. A flat reflection sample is used for determining the pole figure from the center out to about 70". Because of the geometry of the system used, little or no correction for absorption or irradiated volume is necessary.4'6 A separate transmission sample is used for the region near the edge of the pole figure. This procedure requires two separate samples, one of which must be a thin carefully-prepared transmission sample. Furthermore, since the reflection and transmission data are in different arbitrary intensity units, a region of overlap must be obtained, and the intensity data from one set of measurements converted to units of the other. These are serious disadvantages of this method, and they point out the need for a simplified procedure. Since the reflection technique can be used for planes whose normals lie up to about 70° from the sample surface normal, it is apparent that a complete pole figure can be obtained by reflection alone if sample surfaces are cut at oblique angles to the rolling plane Specifically, if a rolled sample is cut so that the normal to the surface formed lies equidistant (54" 44') from the rolling plane normal, rolling direction, and transverse direction, then complete information for one quadrant of the pole figure can be obtained by reflection from the surface. Fig. 1 shows this oblique surface, as well as the position of the pole of this surface in the pole figure. When a surface has been cut oblique to the rolling plane, the standard polar stereographic net is inconvenient to use, and it would be more desirable to have the center of the net coincide with the pole of the oblique plane. Fig. 2 shows such a net, where the center has been offset 54' 44' to correspond to a specimen cut as in Fig. 1. This net was in effect obtained by rotating a standard polar stereographic net 54" 44' with the help of a Wulff net. With the experimental setup used. a sample can be cut from plate of 1/2-in. thickness or br Gen- erally thinner sheet is under investigation, and a composite specimen must be used. A convenient procedure has been to bond together, using epoxy resin, sufficient sheets to form a cube. These are clamped in a vise, and when dry, the whole vise is rotated and a flat surface ground at the required angle. The sample is then mounted inside a larger steel ring using Koldmount, the backside ground flat and parallel to the approximate desired thickness. The sample is then polished and etched to remove any effects of cold working during grinding. With this method only one quadrant of the pole figure is obtained. Often pole figures show symmetry around the rolling and transverse directions, and any slight asymmetry is due to scatter. Should the pole figure not be symmetrical, four oblique surfaces, corresponding to the four quadrants of the pole figure, would have to be examined. In most cases there is symmetry at least around the rolling direction, which reduces to two the number of quadrants to be investigated. For many purposes all that is required is an average polefigure for the four quadrants. This canreadilybe obtained with composite specimens of sheet material, where sheets Corresponding to each of the four quadrants can be intermixed. The four quadrants can be obtained by considering sheet in the normal position, and by rotatiolls of 180" around the sheet normal, the rolling direction, and the transverse direction. If desired, the whole thickness of the sheet can be used, yielding an average of the surface and interior textures; or the surface material can be removed from each sheet, resulting in a pole figure for the center alone. Eugene S. Meieran of the Massachusetts Institute of Technology has independently developed the same method. His results, adapted to a pole figure goniometer with a specimen spiraler, will be described in another publication.

Jan 1, 1962

By C. S. Smith

The solubility of tantalum at 1100°C is 0.025 pct in pure copper, 1.2 pct with 20 pct Ni, and 2.7 pct with -30 pct Ni. The solubility decreases with temperature, and the alloys are precipitation hardenable. A 79/20/1 Cu-Ni-Ta alloy reaches maximum hardness after aging at about 750°C and, if cold worked, does not recrystal-lize below that temperature. The alloys have good tensile properties at moderately elevated temperatures and, since they can be hot and cold worked nearly as easily as cupronickel, they are suggested for service at temperatures above the usual limits for copper alloys. MASSIVE tantalum dissolves extremely slowly in copper-rich alloys, and tantalum powder forms refractory surface layers which prevent its solution unless special precautions are taken. After many trials, an 80 pit recovery was consistently obtained by using a mixture of a finely divided tantalum powder with two or three times its volume of potassium tantalum fluoride (K2TaF1,-melting point about 750°C) poured in a slow stream directly on to the surface of the molten copper alloy, so that each particle would remain coated with flux and be immediately and individually wetted by the molten metal. A 50-50 nickel-tantalum alloy has a melting point of about 1400°C and small lumps of it slowly but satisfactorily dissolve in molten copper-nickel alloys as does commerical "ferro-tantalum." The high affinity of tantalum for carbon makes it necessary to avoid carbonaceous crucibles. COPPER-TANTALUM ALLOYS Castings with good shrinkage resulted when 0.1 pct Ta or more was added to copper melted under charcoal and cast in air. Copper in two-pound melts to which 0.1, 0.15, and 0.2 pct Ta had been added retained residual amounts, by analysis, of 0.025, 0.023 and 0.026 pct, respectively. The solubility of tantalum in molten copper at about 1200 °C is therefore about 0.025 pct. The electrical conductivity of these three samples was 100.48, 100.00 and 100.20 pct IACS in the annealed condition, and 98.24, 97.98 and 98.08 in the cold-drawn condition. Wires 0.080 in. in diam withstood from thirteen to nineteen reversed bends after annealing for 30 min in hydrogen at 850°C and the metal was therefore completely deoxidized. The annealing temperature corresponding to 50 pct loss of work hardness in 1 hr in a strip cold rolled 77 pct reduction was 175C, compared to 230°C for equivalent undeoxidized material. It is unusual for a decrease of recrystallization temperature to result from an alloying addition, and the tantalum probably combines with and removes some minor impurity in the original copper that restrained its recrystalliza- tion. No difficulty whatever was encountered in hot or cold rolling or drawing these ingots, and were tantalum not so expensive it would make an excellent deoxidizer for copper. COPPER-NIcKEL-TANTALUM ALLOYS Studies were made of the solubility of tantalum in a large number of copper-rich alloys, but of these significant solubilities were found only in the case of an iron alloy (which, however, separated into two immiscible liquid layers) and alloys of copper and nickel, in which tantalum is freely soluble and which were found to have interesting properties. The latter alloys are the subject of U. S. Patent No. 2,430,306 (1947). They are not at present available commercially. The Ternary Constitution Diagram—The copper-rich corner of the constitution diagram was constructed on the basis of microscopic examination of samples of various composition and treatments. The alloys were hot rolled to 0.25 in. from castings 0.625 in. thick, then annealed for 1 hr at 1000°C, quenched, cold rolled to 0.10 in. and finally annealed for various periods of time at temperatures between 800" and 1100°C in a nonoxidizing atmosphere and quenched. When the solid-solubility limit had been transgressed, particles of a compound believed to be Ni2Ta*were

Jan 1, 1960

By W. L. Phillips

Stress-train curves were obtained for single crystals of silver, Ag-5 pct Zn, Ag-10 pct Zn, and Ag-20 pct Zn tested in tension and shear at 78°, 195°, and 297°K. At room temperature the critical resolced shear stress gC increased, the length of' the easy-glide region increased, and the rate of' work hardening dwving easy glide decreased with increasixg zinc concentration. The change in the ratio of uc at room temperature to that at lower temperatures was significantly greater for the alloys than for pure silver. It was found that an increment in stress was necessary to continue slip when the slip direction was rotated 60 deg. The magnitude of this increment increased with strain for all alloys, increased with zinc concentration for a given strain, and for a given strain increased with decreasing -temperature. DESPITE its practical importance in improving the mechanical properties, alloying is not fully understood. Except for copper alloys few sets of systematic data are available. Von Goler and Sachs' studied the deformation of Cu-Zn alloys of increasing zinc content and found that, for dilute alloys, the critical resolved shear stress increases linearly with concentration. The range of easy glide was found to increase with increasing zinc content. Schmid and seliger,2 Sachs and Weerts,3 and Osswald4 have shown that with Mg-A1, Au-Ag, and Cu-Ni crystals, respectively, the critical resolved shear stress also varies linearly with concentration. More recently, Linde and his coworkers have investigated the variation of the critical shear stress of copper alloyed with tin , antimony, indium, germanium, silicon, nickel, and gold. They found that the slope of the critical resolved shear stress is related to the change of lattice parameter with composition, and also to the difference in Goldschmidt's atomic diameter between solvent and solute atoms. Garstone, Honey-combe, and creetham6 have shown that similar relationships can be found for small additions of silver, gold, and germanium to pure copper. They found that, with increasing silver or gold concentration, the critical shear stress for glide is increased by alloying, and so is the range of easy glide, which reaches as much as 60 pct for 0.50 pct Ag alloy and 0.62 pct Au alloy, as compared to 6 pct for pure copper of similar initial orientation. They also found that the alloying additions had little effect on the rate of hardening during easy glide, the slope scarcely changing with increasing alloy content. General secondary slip was detected only when the crystals began to harden rapidly. Although the slip appeared to be very fine in the early stages of deformation, coarser slip bands were formed towards the end of the extensive easy-glide range. The present investigation describes the deformation characteristics of single crystals of Ag-Zn containing different concentrations of zinc. Tension and shear testing were used for this study. EXPERIMENTAL PROCEDURE The method of growing the single crystals, sample preparation, and method of testing have been described in detail previously.' EXPERIMENTAL RESULTS A) Tension-Room Temperature. The initial orientations and stress-strain curves of single crystals of silver, Ag-10.0 pct Zn, and Ag-20.0 pct Zn are shown in Fig. 1. It is evident that there is considerable change in the stress-strain characteristics as a function of zinc concentration. The effects of zinc concentration on the critical resolved shear stress for both CU-zn8 and Ag-Zn alloys are summarized in Fig. 2. At all concentrations the resolved shear stress of the Cu-Zn alloys is higher than that of the Ag-Zn alloys. The resolved shear stress increases parabolically as a function of composition for both alloy systems. The length of easy-glide region increased with increasing zinc concentration, Fig. 3b). As the length increased the slope (do/de) decreased slightly, Fig. 3(b). Metallographic investigations demonstrated two significant effects of increasing zinc concentration. First, the amount of clustering increased, compare Figs. 4(a) and (b). The slip lines changed from uniform in pure silver to clustered in the Ag-20 pct Zn and Ag-30 pct Zn alloys. Second, the amount of cross slip decreased as the amount of clustering decreased.

Jan 1, 1968

By J. J. Frawley, W. J. Childs

Experiments were carried out to induce grain refinement during solidification by applying vibrational energy (freq 20 kc) to small specimens of bismuth, tin, and bismuth-tin alloys. The results show that if the intensity of the applied sound -field is not great enough to fragment the growing dendrites of a pure metal, no grain refinement is observed and the pain size of the dynamically nucleated specimens is the same as the grain size of a specimen statically supercooled the same amount. Bismuth specimens did not show any grain refinement; whereas, the tin specimens did show grain refinement. This phenomenon is the result of the difference in growth habit between the bismuth and tin dendrites. The bismuth-tin alloys showed grain refinement and, in addition, the segregation pattern was changed. THE solidification process is a change in phase requiring the nucleation of the solid phase from the liquid and the growth of this solid phase at the expense of the liquid phase. Since many physical properties and also the integrity of a casting are dependent on the solidification process, understanding and controlling this process are very important.' A good example in the controlling of a cast structure using heterogeneous nucleation theory is the reduction of grain size in aluminum castings by nucleation catalysis.2 This mechanism of nucleation catalysis has been explained by Turnbull.3 Another technique for grain refinement, which has received much attention but the mechanism has not been fully understood, is to vibrate the solidifying melt. Vibrations can be applied to the melt either by vibrating the mold directly or by introducing a vibrating rod into the melt.4-13 Three mechanisms have been proposed to explain this phenomenon: 1) The mechanical fragmentation of the original dendrites that grew into the melt. These crystals or fragmented dendrites act as new growth sites. 2) The nucleation of new grains in the liquid by the generation of very high pressure pulses caused by cavitation in the liquid. 3) The remelting of the dendrite arms during the solidification process. This mechanism is operative only in alloy systems and would be enhanced by stirring or mechanical vibration. The purpose of this investigation was to determine the mechanism that will increase the number of grains when mechanical energy is introduced into a solidifying melt. APPARATUS The unit used to generate the ultrasonic vibrations was manufactured by the Redford Co., and is similar to the one used in ultrasonic soldering. Fig. 1 is a sketch of the major components used for generating ultrasonic vibrations. The crystal transducer assembly consisted of four lead zirconate ti-tanate piezoelectric crystals in an aluminum holder. An acoustical horn, which was fabricated from stainless steel, was attached to the holder by a set screw. The resonant frequency of this unit was 20,000 cycles per sec. A Pyrex crucible, 4 in. in diam and 4 in. high, was contained in a hole in the top of the horn. The piezoelectric crystals changed volume when excited by an electric signal, thereby generating a sound signal which passed through the horn. The crucible was coupled to the horn by a liquid silicone oil. The purpose of the couplant was to transmit the soundwaves from the horn to the crucible. Without the couplant, much of the sound energy would be lost. The energy transmitted was sufficient at the resonant frequency used, so that acoustical cavitation always occurred in the molten metal. The presence of acoustical cavitation was detected by the characteristic hissing sound emitted from the liquid. EXPERIMENTAL PROCEDURE The influence of ultrasonic vibration on the grain refinement of bismuth, tin, and bismuth-tin alloys was studied. These metals were chosen because of their low melting temperature and the relative ease with which they can be thermally supercooled. The following procedure was used for obtaining large amounts of supercooling. Pure bismuth (99.999+), which was received in bar form, was mechanically broken into pieces small enough to be accommodated in a 50 ml beaker. About 200 to 300 g of bismuth and a few grams of SnCl2 as a flux were placed in the 50 ml beaker and melted by induction heating. The melt was held for 20 min at

Jan 1, 1970

By I. B. Cadoff, J. C. Bilello, R. Rosenberg

Diffiusion of magnesium into the surface of LiF crystals to controlled depths and subsequent heat treatments provided a wide range of surface zone harahesses and structure, The bend strength of the LiF crystals was increased by as much as an or-dev of magnitude. Ductility was achieved when dislocation generation occurred in the diffusion zone or when dislocations penetrated to the surface from the intevior. A critical surface hardness of 130 to 140 kg per sq mm was found helozu which generation could take place in the diffusion zone and ahoue which the zone was impenetrable, This hardness was obtainable by several methods, among them the aging of quenched MgF2 -LiF solutions to produce MgF, precipitation. Maximum hardness was ohtained in quenched specimens with no visihle evidence of MgF,. Diffusion-zone formation followed a parabolic rate law and an activation energy of 20.9 kcal per mole was obtained for the process. RECENTLY, the properties of ionic crystals as related to surface condition have been receiving much attention, specifically the transitions between ductile and brittle behavior. Originally Joffe 1 showed that NaCl crystals could be made ductile by immersion in water and related this to the elimination of surface microcracks. Aerts and DeKeyser 2 and Gorur 3' have subsequently shown that ionic crystals are inherently ductile and are embrittled through contact with air. Machlin and Murray4 hypothesized that a layer of NaCIO3 produced by contact of ozone with NaCl induced embrittlement by acting as a barrier to outward dislocation flow. westwood,' Rosenberg and Cadoff,9 and Bilello and cadoff' have reported surface strengthening of LiF crystals by coating with a magnesium compound and then heat treating for adherence. The major effect of the coat was to inhibit dislocation-slip lines from reaching the specimen surface. westwoods showed microcrack formation and fracture to be caused by slip-band interactions at the surface. The material presented in this paper is an extension of the work reported earlier by Bilello, Rosenberg, and cadoff'6,7 and illustrates the wide range of surface properties and bulk behavior obtainable by use of heat-treated magnesium-diffused surface regions in LiF crystals. EXPERIMENTAL PROCEDURE The LiF single crystals were obtained from the Harshaw Chemical Co. Some batch to batch variation was observed; therefore all specimens for a given test series were cleaved from the same crystal. The typical dimension used was 1 by 0.1 by 0.40 in. Surface damage resulting from cleavage was removed by chemically polishing in a 2 pct NH4OH solution. Each group of specimens was given a vacuum anneal at 700°C for 4 hr to provide a base standard for measuring comparative effects of various surface treatments. To produce the reacted surface zone, the annealed specimens were immersed in a boiling suspension of MgF, in doubly distilled HzO, agitated slbwly for 30 sec, removed, and dried at room temperature. Uniform coatings of MgF, were deposited with a thickness of approximately 5 mils. It should be noted that this technique can be modified for use with crystals which are soluble in water by using boiling absolute alcohol as the dissolving medium. This was found effective for the coating of NaCl with MgF2. The diffused surface zone was obtained by annealing the coated samples at elevated temperatures in a vacuum of lob4 mm Hg. Penetration depth was controlled by varying the annealing time from 1/2 to 28 hr. After heat treatment, the samples were tested for bend strength and hardness. Load was applied by four-point bending in a hard-beam testing jig. Four-point rather than three-point bending was used to provide a wide area of constant stress and to minimize the effect of localized inhomogenities in the specimen. The deflection rate was 8 x min-' and the distance between knife edges was 1/4 in. Load-time curves were obtained from a chart recorder coupled to the machine and converted to resolved shear stress on the shear plane vs deflection, as plotted in the figures. The unstressed portions of the sample outside of the two outer knife edges were used for the microhardness studies. Microhardness measurements were made with a Bergsman tester attached to a Reichert metallograph. All hardness impres-

Jan 1, 1964

By William Y. Holland, Roger M. Cook

In view of the increasingly widespread deterioration of concrete structures as the result of the interaction of the alkalies sodium and potassium released by hydration of portland cement and susceptible rocks and minerals in aggregates, it is believed that a paper summarizing the geographic distribution of these aggregates will be of interest to producers and users of concrete, concrete products, and concrete-making materials. THIS paper reviews the problem of alkali-aggre-gate reaction in concrete and describes the geologic and geographic occurrence and distribution of alkali-reactive sand and gravel in western United States. It includes no discussion of crushed stone or synthetic aggregates. Most deposits of sand and gravel are accumulations of particles of rocks and minerals from a variety of sources, and it is not unusual for at least one or two varieties of the rocks to contain some form of reactive material. Examination by petro-graphic methods of many sands and gravels, as well as manufactured aggregates, has shown that a comparatively high proportion of the deposits does contain, in greater or lesser degree, rocks and minerals known to be deleteriously reactive with the alkalies of cement. Fortunately the amount of reactive materials is commonly less than that necessary to cause deleterious effects in concrete. As investigation of unsound concrete structures progresses, it becomes evident that the alkali-aggre-gate reaction is even more widespread than supposed, Figs. 1 and 2. Even though some parts of the country appear at present to be immune, further investigations will probably show that the effects of alkali-aggregate reaction can be seen in many structures in these areas, although only on a small scale in most of them. Many concrete structures will, of course, have lived their useful life before disintegration from this cause is serious, and in others the alkali-aggregate reaction may never become significant even though the microscopic evidence of reaction is present. The alkali-aggregate reaction first was reported to be a cause of deterioration of concrete in 1940 when Stanton1 described expansion of concrete pavements in California. Similar expansion and deterioration of concrete was recognized during succeeding years in concrete structures located in many parts of the country, but particularly in the western states. A number of concrete laboratories2 became interested in the problem. It was soon determined that only certain combinations of aggregate and cement caused the alkali-aggregate reaction to take place, and moreover that the reaction progresses only in the presence of water. Further research proved that cements containing more than 0.60 pct total alkalies (pct Na,O + 0.658 x pct K2O), when used with aggregates containing appreciable amounts of reactive ingredients, caused the reaction to take place, usually with subsequent deterioration of the concrete. During the last few years this limitation has been adhered to in both government and private construction as the maximum allowable alkali content of cement to be used with aggregates of known alkali reactivity. Because of this limitation, it appears that deleterious reaction either has been reduced or eliminated in many recently built structures in which it probably would otherwise have occurred. Recent tests have shown that the degree of expansion obtained with any particular cement-aggre-gate combination depends not only on the alkali content of the cement but also upon the relation of this alkali content to the amount and degree of reactivity of reactive constituents in the aggregate.' In laboratory mortar bars, opal and cements with alkali content of as low as 0.2 pct (as equivalent of Na2O) have produced deleterious expansion as the result of alkali-aggregate reaction. These experiments demonstrate that aggregates containing even 0.1 pct of opal are deleteriously reactive. It was soon determined that alkali-silica gels were formed by the interaction of the alkalies of the cement and the reactive aggregate, Figs. 3 and 4. Osmotic or swelling pressures produced by the continued hydration of these gels cause expansion of the concrete with resulting cracking, warping, and dislocation. Evidence of the alkali-aggregate reaction can be seen by a petrographic study of the deteriorated concrete. Among the first structures studied by this method was Parker Dam on the Colorado River, California-Arizona. In the concrete from this dam pebbles of rhyolite, andesite, siliceous limestone, and chalcedonic chert were found to be reactive.

Jan 1, 1954

By C. G. Dunn, P. K. Koh

Microstructure, magnetic torque, and texture data before and after grain growth were obtained on two 3.25 pet Si-Fe specimens having initially the same cold-rolled textures and the same primary recrystallization textures. The latter textures consisted of four components, two only of which were strong; the strong components were near (120) [001] and (320) [001]. The textures of the two specimens obtained by grain growth were different. In one specimen the two weak components were converted into strong components by a secondary recrystallization process; in the other specimen the primary recrystallization texture was retained by a normal grain-growth process. The difference in behavior of the two specimens was interpreted in terms of a difference in the relative grain sizes between weak and strong components; i.e., in terms of a geometrical factor that would alter the early growth rates of grains belonging to the two weak components of the texture. Specifically the growth rate was considered as the product of two terms: a driving force and a boundary mobility. The texture changes observed are considered to favor the oriented-nucleation growth-selectivity theory more than the oriented-growth theory. WHEN primary recrystallization and grain-growth textures form as a result of annealing deformed metals or alloys, the fundamental processes involved are nucleation and growth. Knowledge, therefore, about nuclei and the factors influencing their growth is required not only for the understanding of texture development but also for its control. In the oriented-growth theory of texture formation1, 2, 3 the problem of nuclei is generally disposed of by the assumption that nuclei are available in all orientations; the theory then has to explain the final texture from the initial texture and the way boundary mobility depends on orientation. In the oriented nucleation theory of texture formation"' nuclei are considered to be present only in certain orientations but the importance of growth selectivity is still recognized. For example, the mobility of boundaries of approximately the same orientation and of the coherent type in twins is believed to be low while that of high-angle boundaries, in general, is high. Because of this the theory may be described as an oriented-nucleation growth-selectivity theory. The main feature of the oriented-nucleation theory, however, is the importance given to nuclei; i.e., how they form in specific orientations and how they grow. In the present investigation two cold-rolled single crystals were used to study the effects of growth after primary recrystallization. The cold-rolled textures and the primary recrystallization textures were determined from portions of these specimens and reported earlier.",' The two cold-rolled crystals were in the (111) [112] stable end orientation, the recrystallization textures were nearly identical and consisted of two strong components, designated M and M', which were near (120) [00l] and (320) [00l], respectively, and also some specific weak components near (111) [110] and (111) [110]. It is well recognized that a single strong component in the primary recrystallization texture may be needed for secondary recrystallization3, 5, 8 but unfortunately when this is the case the amount of material left in deviating orientation may be too small either for growth or for positive identification. The present samples proved to be almost ideal for the study of minor components and their influence on texture changes produced by growth after primary recrystallization. The results obtained are interpreted in terms of present knowledge of grain-growth processes. Experimental Procedure Two lots of silicon-iron alloy of essentially the same composition, namely, 3.25 pet Si, 0.004 C, 0.009 P, 0.010 S, 0.035 Mn, 0.070 Ni, 0.090 Cu, 0.009 Sn, with traces of A1 and Cr and the balance Fe, were converted into single crystals 0.025 in. thick and 1.25 in. wide. The orientations were predetermined by the method of reorienting a seed crystal as described elsewhere.3 pecimen 1 from one lot had the (335) [556] orientation while specimen 2 from the second lot had the (111) [112] orientation.* Both crystals were cold rolled to a reduction in thickness of 70 pet while widening approximately 20 pet. Samples of each were selected for determining 1) the cold-rolled texture, 2) the time required at

Jan 1, 1959

By W. C. Hellyer

The papers in this section provide several examples of the application of Process Mineralogy to metallurgical problems. Any experienced metallurgist could cite numerous other examples when process mineralogy has, or could have, provided data of value in his understanding of metallurgical processes. The data developed by mineralogic techniques may supplement conventional chemical analyses, but cannot be replaced by assays. Mineralogic and chemical analyses each provide different types of information. In order for the process mineralogist to interpret his results in the most useful manner, it is desirable that he should have some knowledge of metallurgical processes. Conversely, the metallurgist should have some knowledge of mineralogic techniques to understand the scope and limitations. Mineralogic examinations are time-consuming and expensive. To ensure the effort is not wasted, and indeed does not generate misleading information, the utmost care must be taken at every stage of sampling and sample preparation. The mineralogist may examine microscopically or by x-ray diffraction a one-gram sample representing a flow of possibly thousands of tons per day through a concentrator. Conditions in a concentrator change continually in response to changes in feed rate, feed characteristics, grind, reagent additions, temperature, circulating loads, etc. Lengthy sampling periods are required to ensure the samples examined are representative of average conditions. The sampling program should be drawn up jointly by the metallurgist and mineralogist. Sampling points should be selected with a view to ease of sample cutting. The sampler should be instructed in the method of cutting the samples, the weight or volume of sample to be taken at each cut, the sampling frequency, and sampling period. The sampling period required depends on the scope of the investigation. For example, if a complete survey is to be made of all final and intermediate products of a flotation concentrator, samples should be cut at not more than two-hour intervals, twenty-four hours per day, for not less than one week. For a more limited investigation of one circuit or one section of a concentrator, 'the sampling frequency could be increased to every hour and the sampling period reduced to one or two days.

Jan 1, 1981

By S Li, Y Lei, X Wu, C Ma, W Q. Zhang

The failure of roof of thin bedrock working face under loose aquifer in a coalmine can lead to water-sand inrush disaster. Based on the accident of water-sand inrush in 30108 working face of a mine in Shaanxi province, China, the mechanism of water-sand inrush is theoretically analysed. The process and critical conditions of water-sand inrush in working face are reproduced by numerical simulation where the bedrock thickness is 20 m, the clay layer thickness is 40 m and the mining height is 6.5 m. The study found that under the condition of thin bedrock and thick clay layer, the characteristics of the clay layer have a significant inhibitory effect on the development of the fractured zone, and the development of the water-conducting fractured zone is incomplete and insufficient. However, in the process of continuous mining of multiple adjacent working faces, the strength of the clay is gradually reduced by the influence of mining and the erosion of water, and the height of the fractured zone is gradually increased. In the subsequent mining process of the working face, the roof is more likely to be cut-off and lead to water-sand inrush. From the initial failure of the clay to the final crack directly through the surface, the shear strength of the clay is reduced by about 52 per cent. Further simulation found that in addition to the characteristics of the clay layer itself, the main factors affecting the water-sand inrush in the working face caused by overburden failure also include the difference in bedrock thickness and strength, and the difference in coal seam mining height. With the increase of bedrock thickness, the development height of the fractured zone increases gradually with increases of bedrock thickness when the cutting failure of overburden rock no longer occurs. With the increase of mining height, the height of water flowing fractured zone also increases, but the cracking ratio gradually decreases. Therefore, it’s of great practical significance to systematically study the mechanism and critical conditions of water and sand inrush in mines and the main influencing factors for preventing similar accidents in mines with similar conditions.

Nov 29, 2022

By S. D. Baumer, P. M. Hulme

IN the late thirties, the National Carbide Co. cooperated with C. E. Wood, of the U. S. Bureau of Mines, in his investigation of the relative merits of various desulphurizers, including soda ash, caustic soda, and calcium carbide. Laboratory tests showed that carbide, when it could be made to react, is an excellent desulphurizing agent for molten iron. Sulphur content can be driven to lower levels and higher extractions obtained with carbide than with actionsany of the more common reagents. Wood's results1 are shown in Table I. Unfortunately, as the Handbook of Cupola Operation puts it, the chemical fact that carbide is a good desulphurizer was of only academic interest because it was found to be extremely difficult to devise a practical means to make it react with molten iron. Calcium carbide is formed in the electric furnace at 4000°F and above, and its softening point is probably at least 500 °F above the usual working temperatures encountered in iron and steel practice. Consequently, carbide does not form a true slag but floats as a dry powder on top of the metal and only a very small portion of it ever comes in actual contact with the iron. Stirring with a rabble, or pouring the metal over the carbide, increases the efficiency only slightly. Extractions of 20 to 30 pct can be obtained in this manner, but conventional soda slag treatment can do better than this and do it more cheaply. All attempts to lower the melting point of carbide in order to obtain a reactive, liquid slag have so far proved fruitless. Directly under the arc in a metallurgical electric furnace, carbide becomes highly reactive. Excellent sulphur removal can be obtained without any slag other than a thin layer of carbide." imilarly, good results are obtained by adding small amounts of carbide to the finishing slag in double-slag arc furnace practice. To react a liquid with a solid, it is axiomatic that the liquid has to wet the solid before anything can happen. If the solid is heavier than the liquid, the problem is easy, but it becomes more difficult when the solid is much lighter than the liquid, as in the case of carbide and liquid iron. Wood recognized this problem and solved it in a unique fashion. The results shown in Table I were obtained by spinning the carbide beneath the surface of the molten iron by means of a refractory centrifuge. This technique allowed each particle of the finely divided carbide to come into intimate contact with the metal and to be wetted thereby. Wood's centrifuge technique was successful in the laboratory where it achieved excellent and consistent results. Some attempts were made to expand this method to commercial practice, but serious difficulty was encountered in obtaining a refractory centrifuge head that would be economically feasible. About this time the war intervened and the project lay dormant for several years. In 1944, it was revived. It was suggested that the carbide could be blown into the metal with a carrier gas in an attempt to eliminate the necessity for the expensive and brittle centrifuge. The idea was first tried out in a fairly large ladle of iron using natural gas as the carrier. Considerable sulphur was removed, but it was quite obvious that the use of natural gas was not practical. Attempts then were made to blow carbide into molten iron using, in turn, nitrogen, argon, carbon dioxide, air, and oxygen. The latter two gases proved unsatisfactory. Calcium evidently prefers oxygen to sulphur because in the tests calcium oxide and carbon dioxide were produced, the sulphur still being untouched in the iron. Nitrogen, argon, and carbon dioxide gave much better results, although the efficiencies and extractions were erratic, and only a few isolated tests approached the results obtained by Wood. Table II shows typical results obtained with these gases. The sulphur removals were interesting, sometimes even encouraging, but it is evident that such erratic behavior could not be tolerated in commercial practice. A number of different types of equipment, such as sand blasting machines, refractory guns, and the like can used to blow the solid into the metal. All types required relatively large quantities of gas in order to maintain the flow of solid carbide through the system and into the metal. It was observed that the bubbles of gas breaking through the surface of the metal contained quantities of unreacted carbide. The liquid metal never came in contact with these particles and if it cannot wet them it cannot react with them. The initial work had shown that carbide had great possibilities as a desulphurizer. In practice

Jan 1, 1952

By W. R. Hibbard

THE classical work on the electrical conductivity of alloys was carried out by Matthiessen and his coworkers1 in the early 1860's. He attempted to correlate the electrical conductivity of alloys with their constitution diagrams, but the information regarding the latter was too meager for success. Guertler2 reworked Matthiessen's and other conductivity data in 1906 on the basis of volume composition (an application of Le Chatelier's principle with implications as to temperature and pressure effects), and obtained the following relationships between specific conductivity and phase diagrams (plotted as volume compositions) : 1—For two-phase regions, electrical conductivity can be considered as a linear function of volume composition, following the law of mixtures. 2—For solid solutions, except intermetallic compounds, the electrical conductivity is lowered by solute additions first very extensively and later more gradually, such that a minimum occurs in systems with complete solid solubility. This minimum forms from a catenary type of curve. Intermetallic compound formation with variable compound composition results in a maximum conductivity at the stoi-chiometric composition. Landauer" has recently considered the resistivity of binary metallic two-phase mixtures on the basis of randomly distributed spherical-shaped regions of two phases having different conductivities. His derivation predicts deviations from the law of mixtures which fit measurements on alloys of 6 systems out of 13 considered. Volency (Ionic Charge) Perhaps the first comprehensive discussion of the electrical resistivity of dilute solid-solution alloys was presented by Norbury' in 1921. He collected sufficient data to show that the change in resistance caused by 1 atomic pct binary solute additions is periodic* in character. The difference between the period and/or the group of the solvent and solute elements could be correlated with the increase in resistance. Linde5-7 determined the electrical resistivity (p) of solid solutions containing up to about 4 atomic pct of various solutes in copper, silver, and gold at several temperatures. He reported that the extrapolated"" increase in resistance per atomic percent addition is a function of the square of the difference in group number of the solute and solvent as follows: ?p= a + K(N-Ng)2 where a and K are empirical constants and N and Ng are group numbers of the constituents. This empirical relation was subsequently rationalized theoretically by Mott,8 who showed that the scattering of conduction electrons is proportional to the square of the scattering charge at lattice sites. Thus, the change in resistance of dilute alloys is propor-t,ional to the square of the difference between the ionic charge (or valence) of the solvent and solute when other factors are neglected. Mott's difficulty in evaluating the volume of the lattice near each atom site where the valency electrons tend to segre-gate: limited his calculations to proportionality relations. Recently, Robinson and Dorn" reconfirmed this relationship for dilute aluminum solid-solution alloys at 20°C, using an effective charge of 2.5 for aluminum. In terms of valence, Linde's equation becomes ?P= {K2 + K1 (Z8 -Za)2} A where K1 and K2 are coefficients, A is atomic percent solute, Z, is valence of solvent, and Zß, is valence of solute. Plots of these data for copper, silver, gold, and aluminum alloys are shown in Fig. 1. The values of K1 and K2 are constant for a given chemical period (P), but vary from period to period. The value of K, increases irregularly with increasing difference between the period of the solvent and solute element (AP), being zero when AP is zero. The value of K, appears to have no obvious periodic relationship. All factors other than valence that affect resistivity are gathered in these coefficients. Because of the nature of the coefficients, Eq. 1 is of limited use in estimating the effects of solute additions on resistivity unless a large amount of experimental data are already available on the systems involved. It is the purpose of the first part of this report to investigate the factors that may be included in the coefficients of Linde's equation. On this basis, it is hoped that the relative effects of solute additions on resistivity can be better estimated from basic data, leading to a more convenient alloy design procedure. It is well 10,11 that phenomena that decrease the perfection of the periodic field in an atomic lattice, such as the introduction of a solute atom or strain due to deformation, will also increase the electrical resistivity. Thus, in an effort to relate changes in electrical resistivity to alloy composition, it appears appropriate to consider the atomic characteristics related to solution and strain hardening

Jan 1, 1955

By W. Hurst, R. E. Leeser, W. C. Goodson

Three aspects of gas deliverability are presented in this paper. The first treats with the gas deliverability or availability of a normal depletion-type dry gas field. Such encompasses not only the period of stabilized constant rate, but more so, the "tailings" when a fixed abandonment pressure is reached and the rate by necessity must decline. A comprehensive work plot is offered, developed from mathematics herein included, that removes the triai-and-errnr computations that attended such undertakings in the past. The second part treats with the discount factor of the open flow potential constant from what is observed initially in testing a gas well to what is evidenced when stabilization is reached. This prevails in tight formations, such as the Kansas Hugoton field which is offered as the example. The means of establishing this factor are pressure build-up curves which, as sustained by analytical deductions, reproduce this entire period of transient flow under conditions of a constant rate influx. Finally, what is offered in this paper is the deliverability performance of an exceedingly rich gas condensate field producing from a tight formation. The example shown is the Knox Bromide field in Oklahoma, producing from the Bromide formations. The results are ominous, showing early reduction in permeability to gas pow, due to the retrograde condensate forming in the pore space, with the attending early logging-up of these wells. The analytics of lowered permeability are incorporated in the gas deliverability formula along with the PVT data that gives the increased condensate liquid saturation as the gas flows to the well bore. This paper would not be complete without a critique oflered at the end. With the many gas wells now in production and those that have completed their life, there has been no factual information collected by any source as to what constitutes that permeability range where a gas well would be unimpaired in its gas deliverability by the presence of rich condensate content, and the lowered range where such would be harmful. This question confronts all producers. INTRODUCTION Various aspects of gas deliverability are presented in this paper that includes depletion-type reservoirs, deteriora- tion factor of the gas deliverability constant, and the performance of a rich gas condensate reservoir producing from a tight sand. With respect to the presentation of gas deliverability and its tailings for depletion-type gas reservoirs, one notes that this is essentially the information offered by every gas transmission company and producer appearing before the Federal Power Commission for Letters of Conveyance in the dedication of reserves. In the ordinary procedure, as many engage upon this study, trial-and-error calculations are included, particularly as apply to the tailings. For many years one of the writers has employed mathematical analyses to perform this step and avoid the complexities so associated. In the preparation of this paper these analyses have been amplified to include any slope n for the open flow potential relationship for which the tailings can be determined from Fig. 1. With reference to the deterioration or discount factor of the open flow potential constant as such occurs in the gas deliverability formula, this for the most part has been an unexplored subject. Although the issue first appeared in the Kansas Hugoton field, where such was surmised but only recently resolved, this situation of a deterioration of the gas deliverability constant can occur wherever dry gas production from a tight sand is encountered. The first concerted attacks upon this problem were the presentations of Hurst' and Goodson' before the Kansas Corporation Commission to show that transient fluid flow and unsteady-state flow formulas prevailed. This was amplified later before the Federal Power Commission3 to show that this deterioration factor could be identified from pressure build-up curves. This has been reported by McMahon.4 Its importance to the industry merits the review of these essential features in completing the program on the aspects of gas deliverability. Finally, as illustrated here, for a low permeability formation such as the Knox Bromide field where the gas is rich, representing some 165 bbl of condensate per MMcf of effluent gas, the gas deliverability can be of limited extent in the life of the field, leaving substantial amounts of condensate and gas unrecovered. In cases such as this, gas cycling is mandatory. This is particularly revealed by the fluid mechanics introduced here, employing factual field as well as laboratory data, to show this-restriction upon gas deliverability. PRESSURE DEPLETION What will now be offered is the study of gas deliver-

By R. W. Balluffi, R. Resnick

NUMEROUS investigations of chemical diffusion in a brass have been made and the results are collected in several places.1-3 This work has been mainly concerned with the determination of the chemical diffusivity as a function of composition and temperature. In 1947 Smigelskas and Kirken-dall&apos; showed that zinc and copper diffuse at different rates in face-centered-cubic brass, and since then, a number of efforts have been made to determine the intrinsic diffusivities of zinc and copper in this alloy.1, 5-9 Horne and Mehl8 in particular have recently determined the intrinsic diffusivities as functions of temperature and composition using sandwich-type couples and inert markers. Inman et al." also have determined the intrinsic diffusivities in homogeneous alloys using tracer techniques. When the present work was started, no information of this type was available. Consequently, measurements of the intrinsic diffusivities were made as a function of temperature at a constant composition of 28 atomic pct Zn with vapor-solid diffusion couples where the zinc was diffused into the diffusion couple from the vapor phase. The application of these couples to the study of diffusion in a: brass has been described previously.0,7 The temperature dependence of the intrinsic diffusivities was found to follow the relation D, = A, exp(-Hi/RT) and the values of Hzn, and Hcu, were found to be closely the same. It is emphasized, however, that the chemical dif-fusivity (D = N1D2 + N2D1) is a composite diffusivity and does not necessarily follow this exponential form. It is usually found to do so within experimental error for substitutional alloys because the heats of activation of the intrinsic diffusivities generally are not greatly different.&apos;" Also, at the onset of this work, there was no information available concerning possible unequal diffusion rates of individual components and the existence of a Kirkendall effect in alloys with other than face-centered-cubic structures. Since then, two reports indicating a Kirkendall effect in body-centered-cubic ß brass have appeared. Landergren and Mehl" have published a note describing Kirkendall diffusion experiments with sandwich-type couples. Inman et a1.9 also find a Kirkendall effect in this alloy using the tracer technique. In the present work, several aspects of the Kirkendall effect in ß brass were further investigated using vapor-solid couples. Two different couples were used, one in which the zinc was diffused into the specimen from the vapor phase and the other in which the zinc was diffused out of the specimen into the vapor phase. Briefly, the existence of a Kirkendall effect is confirmed and it is found that Dzn/Dcu = 3 at about the 46 atomic pct composition in this alloy at 600°, 700°, and 800°C. As a result of the unequal diffusion rates of zinc and copper, volume changes occur and subgrain formation is observed in the diffusion zone. In addition, significant porosity is produced by the precipitation of supersaturated vacancies. Diffusion in this alloy is therefore outwardly similar to diffusion in a brass where these effects are also observed, a Brass Experimental Methods—The use of vapor-solid couples in studying diffusion in a brass has been described in previous articles.6,7 The method briefly consists of sealing a copper specimen with Kirkendall markers initially placed on its surface in an evacuated quartz capsule along with a large zinc source of fine a brass chips and then diffusing the zinc into the specimen through the vapor phase. The zinc concentration at the specimen surface rises rapidly enough to a value near that of the a brass source so that the surface concentration may be regarded as constant during diffusion. Under these boundary conditions, values of the chemical diffu-sivity may be obtained by applying the Boltzmann-Matano analysis to the concentration penetration curve, and the intrinsic diffusivities may be obtained from Darken&apos;s5 equations when the velocity of marker movement is known. The diffusion specimens were made from OFHC copper in the form of disks 3.2 cm diam and 0.5 cm thick with faces surface-ground parallel to within +0.001 cm. Markers in the form of fine alumina particles <0.0002 cm diam were placed on the specimen surface. These specimens were then sealed in quartz capsules along with enough a brass chips of a 30.0 atomic pct Zn composition to keep the source concentration from decreasing by more than 0.3 atomic pct Zn as a result of the loss of zinc to the specimen during diffusion. The quartz capsules which were initially evacuated to a pressure of

Jan 1, 1956

By A. B. Cook

Gas cycling is generally considered a much less efficient oil recovery mechanism than water flooding. HOWever, recoveries from some fields have been exceptionally high as a result of gas cycling. Recovery from the Pick-ton field, for example, was calculated to be 73.5 perceni of the stock-tank oil originally in place. In evaluating pressure maintenance projects, determining how much of the recovery is due to displacement by gas and determining how much is due to vaporization of the imrnohile oil in the flow path of the cycled gas is very difficrilt. Even though most of the oil is recovered by displacetr~ent, the success of a project may depend on the amount of oil vaporized. A limited number of experiments have heen performed with a rotating model oil reservoir that simulates gas cycling operations and allows a separation of the oil from, tile free gas flowing into the laboratory wellbore at reservoir conditions, thus revealing which is displaced oil and which is vaporized oil. It Iras been determined that the amount of varporizatio&apos;n is .significant if proper conditions exist These experiments show that oil vaporization depends on pressure, temperature, volatility of the oil and amount of gas cycled. Increases in each of these conditions increase the volume of oil vaporized. Data from six experiments affecting vaporization are presented to illustrate reservoir condition that range from favorable to unfavorable. 111 these eaperitnenis recovery by vaporization ranged from 73.6 to 15.3 percent of /he immobile oil (oil not produced by gas displacerrlt). INTRODUCTION Between 1930 and 1950, gas cycling was a popular. oil recovery practice. especially for the deeper reservoirs. Later, with many case history-type studies published for both gas cycling and waterflooding, it was generally believed that waterflooding was far superior to gas cycling, even when gas cycling was conducted as a primary production procedure by complete pressure maintenance. A good example illustrating the advantage of water-flooding over gas cycling is given in a paper by Matthews&apos; on the South Burbank unit where gas injection was followed by waterflooding. The author concluded in part that "Early application of water injection, without the intervening period of gas injection, would have recovered as much total oil as ultimately will be recovered by waterflooding following the gas injection, and total operating life would have been shortened". This appears to be a logical conclusion. However, it should not be applied to all fields. Pressure maintenance with gas in the Pickton field, as reported by McGraw and Lohec;&apos; will result in a much larger percentage of oil recovery than was obtained in the South Burbank unit. The great success in the Pickton field resulted partly from vaporization of the immobile oil in the flow path of the cycled gas. The amount of vaporization is related to the following conditions: volatility of the oil as reflected by the APT gravity of the stock-tank oil; reservoir temperature; reservoir pressure during gas cycling; and the amount of gas cycled. Therefore, the U. S. Bureau of Mines is investigating these effects on vaporization in a research project using a model oil reservoir. Three different stock-tank oils having 22, 35 and 45" API gravities are being used as base stock to synthesize reservoir oils. Experiments are being performcd to determine vaporization at 100, 175 and 250F and at 1,100, 2,600 and 4,100 psia. This is a progress report showing the results from six experiments. Other Bureau of Mines reports"- concerning vaporization are listed. LABORATORY EQUIPMENT AND PROCEDURES The equipment &apos; consists of an internally chromium-plated steel tube packed with finely sifted Wilcox sand. The tube is approximately 44 in. long and has an ID of 13/4 in. The sand section contains approximately 570 ml of voids, has a porosity of 32 percent, and a permeability to air of 4.3 darcies. A unique feature of the laboratory reservoir (Fig. 1) permits the tube part to rotate at 1 rpm while the outlet and inlet heads are held stationary. The outlet end contains diametrically opposed windows to permit observatlon of the flowing fluids, and two valves, one on the top and the other at the bottom. Oil and free gas. when being produced simultaneously, can be separated by manipulating the two valves to keep a gas-oil interface in view through the windows. Thus, only gas is produced through the top valve and only oil flows through the bottom valve. The laboratory equipment was designed to study vaporization. Therefore, a uniform reservoir was made using dry sifted sand as opposcd to using a consolidated sand core with interstitial water. Furthermore. the reservoir was tilted to minimize fingering of gas. This tilting also in-