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By G. B. Thomas

Several methods of analyzing pressure build-up data in wells have been presented by various authors. This paper reviews the theory and method of D. R. Horner and presents example calculations performed on data obtained by testing several different types of wells. These calculations include, (1) graphical estimation of final static pressure, (2) determination of the productive capacity of the pay away from the well bore and. (3) the degree to which the formation adjacent to the well bore has been damaged by completion or other causes. The methods of testing and precautions which should be taken to assure the best data possible are discussed. Limitations and reliability of calculated results are also treated. INTRODUCTION Pressure testing of wells is generally limited to the determination of producing and static mean formation pressures. The so-called "static" pressure determination.. along with PVT, electric log and production data, enable the reservoir engineer to determine, within reasonable limits, the drive mechanism of the reservoir and in some cases. the amount of edge water encroachment. Producing pressure tests enable calculation of productivity indices and allow the engineer to plan the systematic production of a pool for optimum conservation of suhsurface energy. The radial flow formula advanced by Muskat' has been based on the assumption of incompressible radial fluid flow. It has been known that reservoir fluids do not behave in an ideally incompressible manner. For example, incompressible flow theory indicates a simple logarithmic relationship between the difference of the instantaneous and static well pressures when plotted against time. 'The latter stages of this type of plot of pressure build-up data generally show a marked devia-, tion from the earlier straight line trend. which deviation may be shown to be due to the compressible flow of fluids toward the well bore. Shut-in times of 24, 48. 72. or at most 96 hours are currently in wide use for determining so-called "static" reservoir pressure. Due to the continuation of compressible flow of fluids into the well bore long after this arbitrarily taken shut-in time, the determination of static pressures has almost invariably resulted in lower than equilibrium values. Materials balance calculations made early in the life of a reservoir often result in a calculated reserve which later observations prove to be too low. Failure to obtain reliable "static" reservoir pressures within the prescribed 24 or 48-hour build-up period has undoubtedly been a major factor in obtaining these low estimates. Comparison of theoretical and actual productivity performance has indicated that formation damage and not being able to attain true static pressures have been partially responsible for the observed discrepancies. Research into the theory of compressible flow behavior has resulted in methods of applying these theories to the testing of wells. Application of the developed theories to pressure build-up performance indicates that in many cases the following can be estimated. 1. The static reservoir pressure. 2. The in-place effective formation permeability away from the well bore. 3. The degree or extent by which the formation has been damaged adjacent to the well bore, either through completion methods or subsequent damage due to fluid entry. REVIEW OF THEORY Horner2 has shown that the pressure build-up within a "point source" well is approximated by the following formula: Equation (1) is the approximate "point source" solution to the radial compressible flow equation advanced by Muskat. The solution assumes the following: 1. A point source well is producing at constant rate from the center of an infinite reservoir with a constant pressure at its external boundary. 2. The fluid flowing is present in one phase only. 3. The compressibility and absolute viscosity of the fluid remain essentially constant over the range of temperature and pressure variation encountered. 4. The well i.; shut-in at the sand face arid there is 110 after production into the well bore. 5. The formation permeability is homogeneous in the direction of flow. From Equation (1) it can be seen that if an ideal well were shut-in while producing from a reservoir under the conditions assumed, the pressure build-up would be a logarithmic func-

Jan 1, 1953

By D. C. Hilty, W. Crafts

J. Chipman—It has been my privilege to discuss this work with the authors on several occasions and to observe at first hand the experimental methods employed. I wish, therefore, to emphasize certain points which they have mentioned only briefly with regard to the experimental techniques. The rotating induction furnace as here employed interposes liquid metal between slag and refractory thus preventing the two nonmetallic parts of the system from reaching equilibrium with one another. It is therefore impossible for the metallic phase to be completely in equilibrium with both the slag and the crucible. The metal also acts as a partially permeable membrane allowing certain components, including oxygen, to diffuse from slag to crucible. This transfer results in building up on the face of the crucible a layer of material whose composition is in part dependent on that of the bath. Reactions between the layer and the solid refractory are slow, as evidenced by the rather good life of the crucible. Hence it seems probable that the layer is more nearly in equilibrium with the metal than with the underlying crucible material and that, once it is established under a bath of a given composition, its further reactions with that bath are slow. Additions to slag or bath may be followed by changes in the layer; and time must be allowed for virtual completion of such changes, before it can be assumed that slag and metal are in equilibrium. We may judge from the results reported that, in general, this was the case and that the data represent at least quite close approximations to slag-metal equilibrium. Data on deoxidation and on oxygen solubility are no better than the analytical methods employed. The vacuum fusion method as used by the authors seems entirely adequate for the samples analyzed. I have had frequent occasion to compare results with their laboratory, always with very satisfactory agreement. The determination of aluminum at very low concentrations is perhaps an even more difficult procedure. Here also the colorimetric method used has been worked out with great care and is undoubtedly the most dependable method available. The discrepancy between observed and calculated deoxidation or solubility lines is not to be explained as the result of experimental errors, either in the sampling or analysis of the metal. Nor is it to be blamed upon inaccuracies in the several kinds of indirect data upon which the calculated results were based. It is true that both the observed and the calculated lines admit of some uncertainty as to their exact locations, but the uncertainties are small compared to the wide gap which separates the two lines. The authors have pointed out the real cause of the discrepancy. In all of their experiments the solid phase was not Al2O3 but a mixed oxide containing iron and aluminum. This suggests an extension of the calculated values to include equilibrium with the spinel FeO . A12O3. The free energies of FeO and A12O3 are known, that of the spinel is not. However, it cannot differ greatly from that of its component oxides for even in the more stable spinel, chromite, the free energy of formation from the oxides is less than 10,000 cal. For purposes of calculation we shall call this free energy X and solve for values of X lying between zero and 10,000 cal. The other data required are taken from the forthcoming revision of "Basic Open Hearth Steelmaking" and are given in the following equations in which underlined symbols indicate elements dissolved in liquid steel and the standard concentrations are 1 pct. ?F° at 1600°C, cal ?LA = 2 Al + 3 O; + 107,200 FeO = Fe + 0; + 5,460 FeO + A12O3 = Fe + 2A1 + 4 0; + 112,660 — X The corresponding equilibrium concentrations are shown in fig. 21. The line marked A12O3 corresponds to the first equation, those marked FeO . AL2O3 correspond to the last, with X = 0, 5000 and 10,000 cal, respectively. The two upper lines represent the data of Hilty and Crafts and of Wentrup and Hieber. The points are the observations of Hilty and Crafts in the presence of 0.50 pct Mn.

Jan 1, 1951

By Roy E. Dickerson, W. M. O Connor

The production of crude petroleum of the Bacuranao field, Cuba, fell off rapidly because no new wells Mere drilled. In December 1938, the total was 15 bbl. per day. The estimated average from this serpentine field for the year is 20 bbl. per day. The Motembo area produced an estimated average of 160 bbl. per day. Production in July was 215,946 gal of gasoline, or 165 bbl. per day. In August production was higher because a new well in the concession, the Luisa Marcela, produced 189 drums the first day and required pit storage. The Atlantic Refining Company of Cuba started a deep test upon a long, narrow, surface-defined anticline 3 km. south of Remedios, a town on the north coastal plain of Santa Clara province, in December 1938. The Atlantic Refining Co. is doing extensive seismograph arid gravity-meter work in Matanzas arid Santa Clara provinces. The Shell company was rigging for a deep test in western Havana province at a location about 2 km. west of the town San Antonio dc los Banos New Petroleum Law More serious attention was given by some of the major oil companies to the development of petroleum in Cuba as a, result of the passage of a Petroleum Law ill that country on May 9, 1938. Under the old mining lam of Cuba, which gave no special treatment to petroleum, the usual provisions giving reasonably satisfartory guarantees to encourage investmerit of foreign capital were either entirely lacking or were 30 ambiguously expressed as to require legislative action. Under the new law, Government royalty is fixed at 10 per cent with the provision that it will be reduced to 9 per cent on crude petroleum that is refined in Cuba. Royalty to the surface owner is 1 per cent. A surface tax on a sliding scale from 10¢ to 406 per hectare per year is applicable to all exploitation concessions granted under the law or adapted to its provisions. So export tax is payable upon petroleum. Stability of taxation

Jan 1, 1939

By A. W. Hann

THE importance, to geologists and metallurgists, of knowing the mineralogical forms in which the silver occurs in ores has increased during the past few years, and will continue to increase as long as working hypotheses are converted into proved theories and rule of thumb methods are supplanted by scientific data. The methods used for the determination of these silver minerals have been: (1) careful study of polished ore sections with the microscope, and more recently, (2) metallurgical separation of the ground ore by flotation, tabling and panning, supplemented by microscopic examination of these separated minerals, and chemical analyses. During the course of some experimental work carried on by the testing department of the International Smelting Co. and myself, it became important to determine, in a general way, the distribution of the silver values in the minerals, as they exist in Tintic Standard and North Lilly siliceous oxidized lead-silver ores. These mines are in the East Tintic Mining District, State of Utah. In this work the second method was used. Differential flotation tests were run, separating the sulfide from the oxidized minerals, and the products were assayed. Various concentrates were carefully panned and the separated products assayed; special samples of ore were selected and assayed. The microscope was used only for the purpose of determin; ing whether the individual minerals were in the so-called "free" state. Analysis of Tintic Ores These chemical and mineralogical determinations showed the silver to be present as native silver, argento jarosite, argentite, and combined or inherent in the tetrahedrite, chalcopyrite, galena, pyrite, cerussite, anglesite, mimetite, malachite, iron oxide and occluded in the quartz. Careful microscopic work would probably show other forms in small amounts, such as the halide silver minerals and some of the antimony sulfide combinations. The tabulation of the analyses of the various products (Table 1) shows no evidences of fixed ratios of silver to any particular base metal.

Jan 1, 1929

By Samuel Hoyt

THIS paper gives a brief description of an investigation made several years ago on the diffusion of zinc into copper. The material for that study was furnished in the form of thin copper strips coated with zinc. The result was required rather quickly and at not too great an expense, and especially information was desired as to the rate at which zinc would diffuse from the zinc coating into the copper and the temperature at which the operation should be carried out. A study of the requirements of this problem indicated that the solution might be secured by means of six determinations. This is the smallest number that will give the information desired and, at the same time, furnish checks on the accuracy of the determinations which justify an abbreviated experimental program. This does not count a preliminary test which was designed to give some idea of the correct temperature to use. The minimum number of temperatures that can be used is two. Knowing the rates of diffusion of zinc into copper at two properly chosen temperatures, it is possible to calculate the rate for any other temperature, and also to check the accuracy of the determination by means of the heat of diffusion, which is calculated from the effect of temperature on the rate of diffusion. The minimum number of determinations at any one temperature is three. The amount of diffusion which occurs at a fixed temperature is definitely related to the time of diffusion, so that by determining the amount of diffusion for three different time intervals, this relationship may be established and possibly a check on the accuracy may be secured. This accounts for the six determinations or experiments, and suggests the logical plan of the work. The check used here is not generally applicable to diffusion phenomena, but it seems to hold closely enough for the limited amount of diffusion in this investigation to justify its use.

Jan 1, 1928

By W. M. O Connor, Roy E. Dickerson

The production of crude petroleum of the Bacuranao field, Cuba, fell off rapidly because no new wells Mere drilled. In December 1938, the total was 15 bbl. per day. The estimated average from this serpentine field for the year is 20 bbl. per day. The Motembo area produced an estimated average of 160 bbl. per day. Production in July was 215,946 gal of gasoline, or 165 bbl. per day. In August production was higher because a new well in the concession, the Luisa Marcela, produced 189 drums the first day and required pit storage. The Atlantic Refining Company of Cuba started a deep test upon a long, narrow, surface-defined anticline 3 km. south of Remedios, a town on the north coastal plain of Santa Clara province, in December 1938. The Atlantic Refining Co. is doing extensive seismograph arid gravity-meter work in Matanzas arid Santa Clara provinces. The Shell company was rigging for a deep test in western Havana province at a location about 2 km. west of the town San Antonio dc los Banos New Petroleum Law More serious attention was given by some of the major oil companies to the development of petroleum in Cuba as a, result of the passage of a Petroleum Law ill that country on May 9, 1938. Under the old mining lam of Cuba, which gave no special treatment to petroleum, the usual provisions giving reasonably satisfartory guarantees to encourage investmerit of foreign capital were either entirely lacking or were 30 ambiguously expressed as to require legislative action. Under the new law, Government royalty is fixed at 10 per cent with the provision that it will be reduced to 9 per cent on crude petroleum that is refined in Cuba. Royalty to the surface owner is 1 per cent. A surface tax on a sliding scale from 10¢ to 406 per hectare per year is applicable to all exploitation concessions granted under the law or adapted to its provisions. So export tax is payable upon petroleum. Stability of taxation

Jan 1, 1939

By E. M. Frizzell

Introduction In 1956, the first mobile crusher was installed in a limestone quarry in Hover, Germany. These early mobile crushers solved the problem of wet and soft ground conditions that did not permit the use of haulage trucks due to the high cost of building and maintaining the haulage roads. Quarry operators also wanted to take advantage of continuous belt conveyor haulage systems and the resulting cost savings. European mines, particularly the coalfields, are in soft materials that allow use of bucket wheel excavators and their following continuous haulage system of belt conveyors. Quarry operators, with this background knowledge of belt conveyors in mining, easily accepted the conveyor concept, once in-pit mobile crushing solved the problem of size reduction of mine-run-rock required for conveyor application. Four years after the initial mobile crusher installation, the first report published on the subject appeared in the December 1960 issue of Mining Engineer (Kochanowsky, 1960). With this early background and basis for direction, mobile in-pit crushing and conveying have increased to more than 74 installations. The capacity, type of crusher, and material being processed appear in Table 1. These data in Table 1 indicate that experience to data has been heavily influenced by limestone installations of less than 1 kt/h (1102 stph). Most of these installations were directly fed by a mine face excavator because of the limestone quarry ground conditions. Crusher Configurations Crushers systems developed to date have varying mobility capabilities. These range from fully mobile units that are used continuously in this mode to fixed, permanently located in-pit crushers. The following terms are presented to help distinguish the range of mobility within the configurations of "mobile" crusher systems planned or now in use. Mobile Crusher The crusher works at the mine face, is directly fed by an excavator, and moves in unison with the excavator on its own transport mechanism as the mining progresses. An example is the unit delivered in 1976 to Yamama Cement Co. in Reyadh, Saudi Arabia.

Jan 1, 1986

By J. T. Norton, H. Blumenthal, S. J. Sindeband

The interstitial phases formed by the transition elements with carbon, nitrogen and boron constitute a unique class of substances which are of considerable technical interest because of their well developed metallic properties and their high hardness and melting points. They are also of interest from the point of view of structure. It was pointed out by Hagg1 some years ago that the principal factor determining these structures was the relative sizes of metal and metalloid atoms. He predicted that if the ratio of the radii of metalloid to metal atoms was less than 0.59, the metal atoms would be arranged in a close-packed fashion of relatively simple type. This prediction has been amply confirmed. It appears, however, that this specification applies most generally to those structures in which the metalloid atoms occupy isolated positions in the lattice and there is no tendency for strong binding between the metalloid atoms themselves. The series of borides of the type MeB2 formed from the transition elements of the fourth (Ti, Zr) and fifth (V, Cb, Ta) groups of the periodic table provide an opportunity to investigate this situation further. If one takes as a basis the radius of 0.87 A for the boron radius and the Goldschmidt values for the metal atoms in 12 coordination, then the radius ratio varies from 0.54 for zirconium to 0.64 for vanadium, which latter is considerably greater than Hagg's limit of 0.59. It was of interest, therefore, to see if these five elements would form borides of the MeB2 type and have simple isomorphous structures. When this investigation was initiated, relatively little information had been published on the structure of this group of borides. McKenna2 reported the preparation of ZrB2 by a carbon reduction process. Its structure was hexagonal and the approximate lattice constants were given as a = 3.15 A, c = 3.53 A. Ehrlich3 reported the structure of TiB2 as being of the C 32 type with a = 3.02, c = 3.21 and c/a = 1.06 A. Recently, Kiessling4 published the results on ZrB2, showing it to be one in which the metal atoms are arranged in a simple hexagonal lattice with the boron atoms in flat sheets, midway between the layers of metal atoms. The structure is C 32 type with a = 3.169, c = 3.530 and an axial ratio =1.11 A. He also states that CbB2 and TaB2 are isomorphous with ZrB2. Preparation of Borides The borides of titanium, zirconium, columbium and tantalum were made by the electrolysis of fused salt baths after the method described by Andrieux.5 The bath, totalling about 6500 g in each case had the following general composition: Metal Oxide + B2O3 + CaO + CaF2. The actual proportions of the ingredients were determined for each individual case. Although Andrieux reports the preparation of vanadium boride by the same electrolytic method, several attempts proved unsuccessful. However, it was possible to prepare VB2 by the carbon reduction method used by McKenna to produce ZrB2. The mixture consisted of V2O5 + 6B2O3 + 11C and the reduction was carried out in an induction heated graphite crucible. This method proved satisfactory for ZrB2 and TiB2 and undoubtedly the others could be made in the same way. The borides, which were all in the form of fine gray metallic crystals from the electrolytic bath or gray powders from the reduction process, were carefully separated from other constituents and analyzed chemically for metal and boron content. The densities of the boride powders were measured using a standard 10 cc pyenometer at 18°C and ethyl benzene proved to be the most satisfactory liquid for this purpose. X Ray Technique The boride crystals, as prepared, were too small for single crystal examination so that powder techniques were employed. Patterns of the finely ground borides were prepared, using the Norelco recording X ray spectrometer. The lines on these patterns were indexed with the aid of Hull-Davy charts and the approximate dimensions

Jan 1, 1950

By E. N. Smith, J. C. Redmond

The increasing need for materials capable of withstanding higher operating temperatures for various applications such as gas turbine blading and other parts, rocket nozzles, and many industrial applications, has brought consideration of cemented carbide compositions. The well known usefulness of cemented carbides as tool materials is attributable to their ability to retain their strength and hardness at much higher temperatures than even complex alloys. However, it has been found that the temperatures encountered in cutting operations do not approach by several hundred degrees1 those involved in the applications mentioned above where the interest is in materials possessing strength and resistance to oxidation at temperatures of 1800°F and above. At these latter temperatures, the tool type compositions which are made up essentially of tungsten carbide are found to oxidize very rapidly and to produce oxidation products of a character which offer no protection to the remaining body. As a further consideration, the density of the tungsten carbide type compositions is high, from about 8.0 to 15.0. The refractory metal carbides as a class are the highest melting materials known as shown by Table 1 which summarizes the available data from the literature for the carbides of the elements which are sufficiently available for consideration for these uses. The density is also included in the table, since as mentioned above it is an important consideration in many of the applications for which the materials would be considered. It has been established that in the tool compositions the mechanism of sintering with cobalt is such as to result in a continuous carbide skeleton and that the properties of the sintered composition are thus essen- tially those of the carbide.2 On the hypothesis that this mechanism holds to a greater or less degree in cementing most of the refractory metal carbides with an auxiliary metal, it appears from Table 1 that titanium carbide compositions would offer possibilities for a high temperature material. Titanium carbide has extensive use for supplementing the properties of tungsten carbide in tool compositions. Although the literature contains several references to compositions containing only titanium carbide with an auxiliary metal,3,4,5,6 it may be inferred from the meager data that such compositions were deficient in strength and were considered to have poor oxidation resistance.7 Kieffer, for instance, reports the transverse rupture strength of a hot pressed TiC composition at 100,000 psi as compared to up to 350,000 psi for WC compositions. The work described herein was undertaken to determine the properties of compositions consisting of titanium carbide and an auxiliary metal and to improve the oxidation resistance of such compositions. It appeared possible that the inclusion of one or more other carbides with titanium carbide might improve the oxidation resistance and also that this might be more desirable than other means from the point of view of maintaining the highest possible softening point. Consideration of the available carbides in Table 1 suggests tantalum and columbium carbides because of their high melting points and general refractoriness. The work on improving oxidation resistance was concentrated on the addition of tantalum carbide or mixtures of tantalum and columbium carbide. The auxiliary metals used included cobalt, nickel and iron. It was also desired to learn the general physical properties of these compositions. Experimental Procedure The compositions used in this study were made by the usual powder metallurgy procedure applicable to cemented tungsten carbide compositions. The powdered carbide or carbides and auxiliary metal were milled together out of contact with air. In some cases cemented tungsten carbide balls and in other instances steel balls were used to eliminate any effect of tungsten carbide contamination. A temporary binder, paraffin, was then included in the mix and slugs or ingots were pressed with care to obtain as uniform pressing as possible. The ingots were presintered and the various shapes of test specimens were formed by machining, making the proper allowance for shrinkage during sintering. Thereafter the shapes were sintered in vacuum at temperatures of from 2800 to 3500°F. Final grinding to size was carried out by diamond wheels under coolant. The titanium carbide used contained a minimum of 19.50 pet total carbon and a total of 0.50 pet metallic impurities as indicated by chemical and spectrographic analysis. It was found by X ray diffraction examination with

Jan 1, 1950

By A. E. Lee

THE Blackwell Zinc Co., Inc., a subsidiary of the American Metal Co., Ltd., operates a horizontal retort zinc smelter at Blackwell, Okla. The plant has 14 furnace blocks of 800 retorts each, fired with natural gas on a 48 hr cycle. Over 13,000 tons of zinc-bearing material, chiefly sulphide flotation concentrates, are treated monthly to produce slab zinc and high lead-cadmium fume. In 1942 a program of rebuilding and modernizing the smelter was started. By 1947 furnace smelting capacity had been increased to a point where roasting and sintering facilities were inadequate, and it was necessary to purchase oxidized materials to supplement sinter production. The seven 210 ft Ropp roasters and three 42 in. x 44 ft Dwight-Lloyd machines then in use had been in service at least 20 years and were in need of major rebuilding. Thus it was entirely practical to consider all new equipment and a change of method rather than rebuilding and repairing obsolete units. A study of the problem indicated that roasting as such could be eliminated and roasting and sintering accomplished in one step by a modification of the Robson process,' which had been used since the early 1930's by the National Smelting Co., Ltd., at their plants at Avonmouth, England, and Swansea Vale, South Wales. Francis P. Sinn, General Manager, Zinc Smelting Operations, The American Metal Co., Ltd., who was familiar with the practice in England, suggested the use of one large machine for the entire operation from concentrate to sinter. One step sintering appeared to best meet Blackwell's plant requirements and indicated substantial savings in labor, gas, coal, and repair costs. Choice of Machine Size The sinter machine size was set at 12x168 ft for a rated capacity of 540 tons per day. This tonnage, produced on a five day week, would meet the seven day requirements of the 14 furnace blocks. The one large machine was quoted at a lower cost than two or more 6 ft wide machines of similar total capacity. Further, the larger machine could be housed in a smaller structure and only one set of equipment for charge preparation and delivery and for disposal of sinter cake was needed. One machine on a five day week made possible a concentration of the skilled operating personnel and required less men than a plant including two or more machines and related equipment circuits. Fewer units of equipment meant less maintenance, and the two down days weekly allowed ample time to repair and, if necessary, to make up lost production. Experience had indicated better sintering quality and rates with larger masses of material, not only on wider machines, but also in deeper beds. The ratio of windbox perimeter to area for the 12x168 ft machine is 0.179, compared to 0.353 for a 6x102 ft machine and 0.617 for a 42 in. x 44 ft machine. This meant less air leakage with resulting fan power savings and less spoilage of charge along the pallet sides. Performance Initial operation of the new sinter plant was made in November 1951 and regular production attained late in December. The average product sinter output during 1952 and the first half of 1953 has been 18.2 tons per hr. The average for one month has been as high as 22.4 tons per hr. Considerable experimenting with varied operating conditions accounts in part for the below capacity — 24 tons per hr — average output, and work to further improve production rate continues. A typical sinter analyses is 66.0 pct Zn, 0.3 pct Pb, 0.1 pct Cd, 0.3 pct S, 8.0 pct Fe, 2.0 pct SiO,, 0.8 pct CaO, and 0.2 pct MgO. Use of this material has made possible increases in furnace burden and improved furnace operation over the former practice using sinter made from Ropp roasted concentrates. Better lead and cadmium elimination in sintering has permitted the furnace production of slab zinc lower in lead and cadmium. Anticipated economies of operation have largely been gained. The sinter plant is operated by seven men per 8 hr shift — one head operator, three equipment operators and three sweepers — plus one oiler on day shift only. While it has been necessary at times to operate seven days a week to produce the required sinter tonnage, the five day work week usually has been adequate. Consumption of natural gas for sinter bed ignition is 200,000 to 300,000 cu ft per day. Green Ore Sintering Practice The 30 to 31 pct sulphur content of the —200 mesh zinc concentrates is the fuel used to sinter the charge, no coal addition being required. In the feed to the machine, sufficient concentrates are added to crushed return sinter fines containing 0.3 to 0.5 pct sulphur to produce a charge averaging 5.0 to 6.5 pct sulphur. Since the return sinter used in Blackwell's practice is varied from — 1/2 to — 1/8 in., the actual sintering mixture of fine sinter and concentrates is somewhat higher in sulphur. The coarser sinter particles are too large to resinter and merely aid porosity in the sinter bed. The ratio of concentrates to return sinter in the charge ranges from about 1:4 to 1:5.5. Variations are based on the appearance of pried up bed sections, bed exit gas temperature trends, windbox suctions, and return sinter size. Sufficient sulphur must be used to obtain fritting of the charge into a soft sinter cake and to aid in the elimination of lead and cadmium. Excessive feed sulphur will result in partial slagging of the cake impairing porosity and prolonging sintering time.

Jan 1, 1954

By M. Gensamer

In applied mechanics and in metallurgy the transition from elastic to inelastic action is a matter of considerable interest and importance. Often the first inelastic deformation is apparently quite homogeneous; that is, uniformly distributed throughout the specimen. Sometimes this deformation is heterogeneous; that is, localized; inelastic deformation proceeds to some definite amount in restricted regions before adjacent regions of the specimen are inelastically deformed. In such cases the deformation does not become homogeneous until the whole specimen has been deformed the amount corresponding to that for each localized deformation. If the test is stopped before uniform extension sets in, the heterogeneous character of the deformation is apparent on the surface of the specimen through characteristic markings, which have been called "LÜders'" lines, "Hartmann's" lines, the "Piobert effect," or simply "flow figures." These markings are the source of considerable trouble in fabricating operations, particularly in the deep drawing of steel sheet. In many cases where the transition is of this nature, the stress developed at the upper limit of the elastic range is greater than the stress during the period of heterogeneous deformation, giving rise to the familiar "drop of the beam" effect in testing. The amount of the yield-point elongation, as well as the value of the stress at the lower yield point (the value to which the stress drops when yielding begins), are functions of the temperature and the testing speed. Lower temperatures and faster rates of testing increase both the yield-point elongation and the yield-point stress. These matters have been ably discussed in a recent paper by Winlock and Leiterl though, as brought out by the discussion of that paper, the phenomena are but little understood. The purpose of the present paper is to clarify the problem through the application of a simple principle, and to show that, through the application of this principle, a number of phenomena in the plastic deformation of metals become more readily understood. The principle is this: During homogeneous flow, the rate of work-hardening is greater than the rate of change of stress resulting from change

Jan 1, 1938

By M. Gensamer

In applied mechanics and in metallurgy the transition from elastic to inelastic action is a matter of considerable interest and importance. Often the first inelastic deformation is apparently quite homogeneous; that is, uniformly distributed throughout the specimen. Sometimes this deformation is heterogeneous; that is, localized; inelastic deformation proceeds to some definite amount in restricted regions before adjacent regions of the specimen are inelastically deformed. In such cases the deformation does not become homogeneous until the whole specimen has been deformed the amount corresponding to that for each localized deformation. If the test is stopped before uniform extension sets in, the heterogeneous character of the deformation is apparent on the surface of the specimen through characteristic markings, which have been called "LÜders'" lines, "Hartmann's" lines, the "Piobert effect," or simply "flow figures." These markings are the source of considerable trouble in fabricating operations, particularly in the deep drawing of steel sheet. In many cases where the transition is of this nature, the stress developed at the upper limit of the elastic range is greater than the stress during the period of heterogeneous deformation, giving rise to the familiar "drop of the beam" effect in testing. The amount of the yield-point elongation, as well as the value of the stress at the lower yield point (the value to which the stress drops when yielding begins), are functions of the temperature and the testing speed. Lower temperatures and faster rates of testing increase both the yield-point elongation and the yield-point stress. These matters have been ably discussed in a recent paper by Winlock and Leiterl though, as brought out by the discussion of that paper, the phenomena are but little understood. The purpose of the present paper is to clarify the problem through the application of a simple principle, and to show that, through the application of this principle, a number of phenomena in the plastic deformation of metals become more readily understood. The principle is this: During homogeneous flow, the rate of work-hardening is greater than the rate of change of stress resulting from change

Jan 1, 1938

By M. Gensamer

IN applied mechanics and in metallurgy the transition from elastic to inelastic action is a matter of considerable interest and importance. Often the first inelastic deformation is apparently quite homogeneous; that is, uniformly distributed throughout the specimen. Sometimes this deformation is heterogeneous; that is, localized; inelastic deformation proceeds to some definite amount in restricted regions before adjacent regions of the specimen are inelastically deformed. In such cases the deformation does not become homogeneous until the whole specimen has been deformed the amount corresponding to that for each localized deformation. If the test is stopped before uniform extension sets in, the heterogeneous character of the deformation is apparent on the surface of the specimen through characteristic markings, which have been called "Lüders"' lines, "Hartmann's" lines, the "Piobert effect," or simply "flow figures." These markings are the source of considerable trouble in fabricating operations, particularly in the deep drawing of steel sheet. In many cases where the transition is of this nature, the stress developed at the upper limit of the elastic range is greater than the stress during the period of heterogeneous deformation, giving rise to the familiar "drop of the beam" effect in testing. The amount of the yield-point elongation, as well as the value of the stress at the lower yield point (the value to which the stress drops when yielding begins), are functions of the temperature and the testing speed. Lower temperatures and faster rates of testing increase both the yield-point elongation and the yield-point stress. These matters have been ably discussed in a recent paper by Winlock and Leiter1 though, as brought out by the discussion of that paper, the phenomena are but little understood. The purpose of the present paper is to clarify the problem through the application of a simple principle, and to show that, through the application of this principle, a number of phenomena in the plastic deformation of metals become more readily understood. The principle is this: During homogeneous flow, the rate of work-hardening is greater than the rate of change of stress resulting from change

Jan 1, 1938

By L. W. Kemph, K. R. VanHorn

During the recent development of aluminum alloys for free-cutting screw-machine rod, it became desirable to know something of the solubility of lead and bismuth in liquid aluminum and in some aluminum alloys. The literature is not particularly helpful in supplying this information. These portions, therefore, of the constitutional relationships of aluminum-bismuth and aluminum-lead alloys were investigated by thermal analysis and by chemical analysis of samples taken from aluminum-rich melts in equilibrium with precipitated lead or bismuth. The solubility of lead and bismuth in some liquid aluminum-copper alloys was also investigated. Some consideration was also given to the solubility of these elements in solid aluminum. Among the earliest investigators of the aluminum-lead and alunlinum-bismuth systems was Wright,' who reported that melts of aluminum and lead formed two layers indicating limited liquid solubility. Under his conditions, the aluminum-rich layer was reported to contain 1.91 per cent Pb and the lead-rich layer, 0.07 per cent Al. Subsequently, Pecheau2 found that in aluminum-rich alloy melts with more than 10 per cent Pb three layers were distinguishable. He reported that the middle layer contained from 3 to 10 per cent Pb. He also found that the melting point of aluminum appeared to be lowered slightly by the addition of lead. Gwyer3 investigated these alloys and found evidence of a slight lowering of the freezing point of aluminum by the addition of either lead or bismuth. He found no evidence of solid solubility in either case and made no attempt to determine the liquidus curves. Hansen and Blumen-tha14 reported that the addition of lead distinctly lowered the solidification point of aluminum. They also found that bismuth lowered the melting point of aluminum. Guillet5 reported almost complete mutual immiscibility for the aluminum-bismuth alloys in the liquid state. Bohner6 examined the effect of various concentrations of lead and bismuth on the electrical conductivity of aluminum. He found decreases in conductivity on annealing at 500' C. as compared with the conductivity of the same alloys on annealing at 300' C.

Jan 1, 1939

By L. W. Kemph, K. R. VanHorn

During the recent development of aluminum alloys for free-cutting screw-machine rod, it became desirable to know something of the solubility of lead and bismuth in liquid aluminum and in some aluminum alloys. The literature is not particularly helpful in supplying this information. These portions, therefore, of the constitutional relationships of aluminum-bismuth and aluminum-lead alloys were investigated by thermal analysis and by chemical analysis of samples taken from aluminum-rich melts in equilibrium with precipitated lead or bismuth. The solubility of lead and bismuth in some liquid aluminum-copper alloys was also investigated. Some consideration was also given to the solubility of these elements in solid aluminum. Among the earliest investigators of the aluminum-lead and alunlinum-bismuth systems was Wright,' who reported that melts of aluminum and lead formed two layers indicating limited liquid solubility. Under his conditions, the aluminum-rich layer was reported to contain 1.91 per cent Pb and the lead-rich layer, 0.07 per cent Al. Subsequently, Pecheau2 found that in aluminum-rich alloy melts with more than 10 per cent Pb three layers were distinguishable. He reported that the middle layer contained from 3 to 10 per cent Pb. He also found that the melting point of aluminum appeared to be lowered slightly by the addition of lead. Gwyer3 investigated these alloys and found evidence of a slight lowering of the freezing point of aluminum by the addition of either lead or bismuth. He found no evidence of solid solubility in either case and made no attempt to determine the liquidus curves. Hansen and Blumen-tha14 reported that the addition of lead distinctly lowered the solidification point of aluminum. They also found that bismuth lowered the melting point of aluminum. Guillet5 reported almost complete mutual immiscibility for the aluminum-bismuth alloys in the liquid state. Bohner6 examined the effect of various concentrations of lead and bismuth on the electrical conductivity of aluminum. He found decreases in conductivity on annealing at 500' C. as compared with the conductivity of the same alloys on annealing at 300' C.

Jan 1, 1939

By Tracy Jarrett

THE alloying of various elements with gold to produce different colors is an old art, but the effect of each element or combination of elements is not generally known. Investigations have been made in this field by F. E. Carter,1 E. M. Wise,2 and L. Sterner-Rainer.3 It is the intent of this paper to present in schematic diagrams the effects of various ele¬ments upon the color and the melting point of gold alloys. In this investigation 2-oz. melts made in a high-frequency induction furnace were used for all tests. The melting points were determined by the use of a calibrated chromel-alumel thermocouple sealed in a thin-walled alundum tube. The couple was then submerged in the molten metal and the freezing and melting points were determined by using a Leeds and Northrup potentiometer. By checking several melts using copper, zinc and gold, it was found that the accuracy of determining the melting point was within ± 5° F. To determine the differences in colors and to classify them, a wet tissue paper was placed over the polished samples and examined under a uniform white light. The 2 by ½ by 0.045-in. samples were cut from 50 per cent cold-worked strip. The original ingot was 3 by ¼ by ¾ in. This visual comparison, although not scientifically exact, served as a quite satisfactory means for determining and classifying these differences. The base alloys, or "hardeners," were first made up and analyzed, after which the gold and silver were added. This method of making up the alloys was chosen so that the same base alloy could be used for the gold alloys of different karats. The first series consisted of gold, copper, zinc and nickel, the copper comprising from 85 to 65 per cent of the content of the "hardener" and the zinc and nickel replacing copper. The second series consisted of gold, silver, copper, zinc and nickel, the copper comprising from 85 to 65 per cent of the content of the hardener with the silver, nickel and zinc replacing copper. There was no particular reason for choosing these combinations, except that they gave a color range from red-pink to white.

Jan 1, 1939

By Walter R. Hibbard, George H. Eichelman, William P. Saunders

INTEREST in the various products of the austenite eutectoid transformation in iron-carbon alloys, particularly as produced by the isothermal sub-critical techniques introduced by Davenport and Bain,1 has resulted in the application of similar heat treatments to other eutectoid transformations. Studies2.3.4 of the beta copper-aluminum alloy eutectoid transformation revealed microstructures very similar to those found in iron-carbon alloys. Investigations5,6 of the kappa phase in the copper-silicon alloy system have established the eutectoid type transformation of this phase into terminal alpha and intermediate gamma phases. This transformation has been reported' as forming a eutectoid type structure in a very sluggish manner by a long time isothermal treatment. The purpose of the present investigation is to study the products of the kappa eutectoid transformation as affected by transformation temperatures by means of microscopic and hardness methods. PREPARATION OF ALLOYS The copper-silicon alloy equilibrium diagram is shown in Fig I. The kappa field converges to a minimum silicon solubility at the eutectoid composition and all other completely kappa alloys are hypereutectoid. Thus, kappa decomposition involves first the proeutectoid precipitation of gamma, followed by the eutectoid transformation of a lower silicon content kappa (5.2 pct). Smith5 has indicated that alloys containing between 5.4 and 5.7 pct silicon could be hot rolled, but that the latter composition was desirable in order to permit a wider kappa temperature range. The alloy was prepared by adding Baker's commercially pure silicon to an ingot of copper-silicon alloy containing 2.34 pct silicon remaining from the investigation of Brick, Martin and Angier.7 Following the casting techniques of Krynitsky, Saunders and Stern,8 the ingot was melted under a heavy layer of dried charcoal in a clay-graphite crucible in a gas-fired pot furnace. Small lumps of silicon were held under the melt surface with a graphite rod. After the silicon had dissolved, the alloy was chill-cast and then remelted without a cover, stirred thoroughly, skimmed and poured into a preheated cast iron mold. The cast microstructure is shown in Fig 2. The casting, 10 X 4 X ¾ in., was annealed at 750°C for 21 brand furnace cooled. About 1/16 in. was milled from all surfaces. The plate was cut in half longitudinally and the bottom half analyzed by A.S.T.M. methods.9 The composition by weight was as follows: copper 94.24 pct, silicon 5.56 pct, iron 0.11 pct.

Jan 1, 1948

By Tracy C. Jarrett

The alloying of various elements with gold to produce different colors is an old art, but the effect of each element or combination of elements is not generally known. Investigations have been made in this field by F. E. Carter,' E. M. Wise,2 and L. Sterner-Rainer.3 It is the intent of this paper to present in schematic diagrams the effects of various elements upon the color and the melting point of gold alloys. In this investigation 2-oz. melts made in a high-frequency inductiorl furnace were used for all tests. The melting points were determined by the use of a calibrated chromel-alumel thermocouple sealed in a thin-walled alundum tube. The couple was then submerged in the molten metal and the freezing and melting points were determined by using a Leeds and Northrup potentiometer. By checking several melts using copper, zinc and gold, it was found that the accuracy of determining the melting point was within ± 5" F. To determine the differences in colors and to classify them, a wet tissue paper was placed over the polished samples and examined under a uniform white light. The 2 by 45 by 0.045-in. samples were cut from 50 per cent cold-worked strip. The original ingot was 3 by % by % in. This visual comparison, although not scientifically exact, served as a quite satisfactory means for determining and classifying these differences. The base alloys, or "hardeners," were first made up and analyzed, after which the gold and silver were added. This method of making up the alloys was chosen so that the same base alloy could be used for the gold alloys of different karats. The first series consisted of gold, copper, zinc and nickel, the copper comprising from 85 to 65 per cent of the content of the "hardener" and the zinc and nickel replacing copper. The second scries consisted of gold, silver, copper, zinc and nickel, the copper comprising from 85 to 65 per cent of the content of the hardener with the silver, nickel and zinc replacing copper. There was no particular reason for choosing these combinations, except that they gave a color range from red-pink to white.

Jan 1, 1940

By Tracy C. Jarrett

The alloying of various elements with gold to produce different colors is an old art, but the effect of each element or combination of elements is not generally known. Investigations have been made in this field by F. E. Carter,' E. M. Wise,2 and L. Sterner-Rainer.3 It is the intent of this paper to present in schematic diagrams the effects of various elements upon the color and the melting point of gold alloys. In this investigation 2-oz. melts made in a high-frequency inductiorl furnace were used for all tests. The melting points were determined by the use of a calibrated chromel-alumel thermocouple sealed in a thin-walled alundum tube. The couple was then submerged in the molten metal and the freezing and melting points were determined by using a Leeds and Northrup potentiometer. By checking several melts using copper, zinc and gold, it was found that the accuracy of determining the melting point was within ± 5" F. To determine the differences in colors and to classify them, a wet tissue paper was placed over the polished samples and examined under a uniform white light. The 2 by 45 by 0.045-in. samples were cut from 50 per cent cold-worked strip. The original ingot was 3 by % by % in. This visual comparison, although not scientifically exact, served as a quite satisfactory means for determining and classifying these differences. The base alloys, or "hardeners," were first made up and analyzed, after which the gold and silver were added. This method of making up the alloys was chosen so that the same base alloy could be used for the gold alloys of different karats. The first series consisted of gold, copper, zinc and nickel, the copper comprising from 85 to 65 per cent of the content of the "hardener" and the zinc and nickel replacing copper. The second scries consisted of gold, silver, copper, zinc and nickel, the copper comprising from 85 to 65 per cent of the content of the hardener with the silver, nickel and zinc replacing copper. There was no particular reason for choosing these combinations, except that they gave a color range from red-pink to white.

Jan 1, 1940

By G. Gutzeit

An inner complex is a cyclic chemical structure containing an inorganic cation that is bound simultaneously to several atoms in a single organic molecule; on the one hand by means of ordinary valence bonds (electron exchange), on the other hand through the action of the electric field thus created, which satisfies the so-called secondary valences. The relative positions of the salt-forming and complex-forming groups are such that most frequently a four, five, or six-membered ring results through this double attachment of the cation.1-6 The formation of inner-complex ring systems depends not only upon the nature and suitable position of the salt-forming and complex-forming groups for ring closure, but, to a great extent, also on the nature of the metallic cation entering the reaction. This selective character of chelate-forming organic compounds is one of their most interesting and most valuable properties. As a matter of fact, the largest number of their practical applications is based upon their specificity.4,7-l3 Once a chelate compound is formed, its character is definitely "organic" in nature. In other words, its properties are conditioned to a much larger degree by the carbon chains or rings than by the metallic atom. Many inner complexes are soluble in nonpolar solvents such as benzene, paraffin oil or carbon tetrachloride, while the chelate-forming reagent before closure of the metal-organic ring is water soluble. (Example: copper complex of salicyl-aldoxime') It is obvious that such particular properties as those indicated above can be utilized whenever specificity and practically complete binding of inorganic ions into an undissociable complex are required. One of the well-known applications of chelate-forming compounds has been the development of specific reagents in analytical chemistry, creation of the spot-test method,4,14-16 and the application of the same principles to the contact print method for determining minerals." Chelate-forming Compounds as Collectors In the field of flotation, where selectivity is often a quality of paramount importance for the collector, various workers have lately attempted to apply their knowledge of specific organic analytical reagents to this purpose. A. C. Vivian18 has concentrated cassiterite by using ammonium nitrosophenylhydroxyl-amine (Cupferron) C6H5NO(=NONH4). Holmanl9 has tested dimethylglyoxime for the flotation of nickel oxide minerals, while deWitt has shown in a series of systematic experiments that alpha-diox-imes were generally selective collectors for nickel ores. Taurin NH2(CH2)2S03H has been proposed for the concentration Of Oxidized lead ores.19 Diphenylthio-carbazone

Jan 1, 1947