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By J. J. Lander, L. H. Germer

MOLYBDENUM and tungsten have desirable corrosion and temperature resistant properties, but the metals in bulk are expensive and their fabrication is difficult. Such considerations led to a search for a method of plating them upon base metals. This search was successful and led furthermore to a number of developments which could not have been foreseen. Neither pure tungsten nor pure molybdenum has been electroplated successfully, although the literature of electroplating is liberally sprinkled with the description of unsuccessful attempts. The process of plating these metals by thermal reduction of their halides has achieved only limited usefulness because of technical limitations and because of limited range of product quality. Plating by thermal decomposition of the carbonyls does not suffer from limitations of the same sort and the properties of the plate are readily controllable. This paper describes the plating of molybdenum and tungsten, and of compounds and alloys of these metals, by pyrolysis of their carbonyl vapors. Chromium also has been plated in this manner, but the experiments upon chromium have been less extensive and the results much less satisfactory. Probably the most important of the products which we have obtained are the alloys with carbon, and the carbides of the metals. Either molybdenum or tungsten can be deposited upon a base metal as a coherent and adherent coating. By adjusting the plating condition the carbon content of the coating can be made to have any value from substantially zero to about 35 atomic pct. The hardness is dependent primarily upon the amount of carbon in the plate and can be regulated over a very wide range, some coatings containing considerable carbon being harder than sapphire. In addition to products already known this method of plating has yielded new carbides of molybdenum and tungsten and alloys supersaturated with carbon. These new products are possible because, in the process of plating, carbonyl can be decomposed at temperatures as low as about 150'C, and thus in the presence of other substances reactions occur which could perhaps not be produced in any other way. In addition to carbides and alloys with carbon, sulphides and oxides of molybdenum and tungsten have been produced and studied. There are certain other advantages of the carbonyl method of plating. It is not required that the base have good electrical conductivity as in electrochemical processes, and the base need not have the temperature stability required in plating from a halide. Thus low melting glasses, as well as other ceramics, can be plated almost as readily as metals. In particular, the plating of glass with

Jan 1, 1947

By T. H. Alden, H. W. Schadler

The strain rate dependence of the flow stress of the eutectoid Zn-Al alloy has been determined as a function of mechanical processing, microstructure, and temperature. The best superplastic properties result from the ultrafine, equiaxed structure produced by solution treatment and isothermal transformation at 0°C. Lamellar structures produced by isothermal transformation and coarse equiaxed structures produced by annealing also exhibit strain rate sensitivity in excess of 0.5, but at higher stresses and lower strain rates than the finest structure. Solution treatment and isothermal transformation eliminate the effect of prior processing history. Small composition variations in the binary alloy do not influence the mechanical properties. Below the eutectoid transformation temperature (.275C) increasing temperature lowers the flow stress at all strain rates. The data do not favor any of the present proposals for the mechanism of superplastic flow. ALLOYS of zinc and aluminum, near the eutectoid composition, have been investigated for: 1) the flow stress-strain rate and elongation behavior,1, 2) the transformation kinetics,3 and 3) structure,3"5 but the structure sensitivity of the mechanical properties is poorly understood. Using a near eutectoid alloy water-quenched from 380°C, Backofen et aL2 estab- high and increases with increasing strain rate. They found a correlation between strain rate sensitivity and tensile elongation as expected from the increased resistance to necking that a high strain rate sensitivity provides.296 The large elongation at high strain rates is attractive for metal forming. Since most other superplastic alloys7-l3 do not show high strain rate sensitivity at such a high strain rate (for the exception see Ref. 12) there is the possibility of a unique deformation mechanism for this alloy. The sensitivity of the mechanical properties of the eutectoid alloy to thermal history1 suggests a structure sensitivity that has not been demonstrated. Gar-wood and Hopkins3 identified a lamellar product for material transformed between 200" and 260°C. The size of the lamellae decreased with decreasing temperature. They also demonstrated that an unresolved transformation product formed below 200°C. A granular two-phase material was resolved for specimens quenched to below 150°C by Mitbauer and sauerwald4 who observed coarsening of the structure after annealing. The role of grain boundaries in superplastic deformation is suggested by the strong effect of grain refinement in encouraging this phenomenon at high strain rateS7-11, 13 and is emphasized in several proposals about rnechanism7, 8, 12 and in a theory14 of high-temperature deformation. Alden8 showed metallographic evidence that grain boundary sliding is occurring extensively at strain rates where m is large but less at high strain rates where normal plasticity is observed. Holt and Backofen10 have shown that sliding also oc-

Jan 1, 1969

By M. G. F. Söhnlein

IN THE metallurgical treatment of sulfide silver-tin ores mined at Oruro, Potosi, and Chocaya, the most important and difficult step is chloridizing-roasting. The ores are chiefly mined from veins in rhyolite, a detailed description of which can be found in most textbooks on ore deposits. The chief gangue minerals are Pyrite and quartz, and the silver content is derived from tetrahedrite, jamesonite, stibnite, and cylindrite. Most of the tin is present in the form of a rather impure cassiterite, which forms microcrystalline aggregates of varying richness with quartz and pyrite; occasionally, some tin is found as stannite, cylindrite, and other complex sulfantimonates. The silver content of the minerals that compose the ore is approximately as follows: Pyrite, 3 to 5 oz. per ton; jamesonite, 30 to 50 oz. per ton; stibnite, 30 to 150 oz. per ton; cylindrite, 200 to 300 oz. per-Jon; tetrahedrite, 500 to 3000 oz. per ton. Occasionally, some ruby silver ore is found, but it is very rare. In the mines of Oruro, which are the deepest in the sulfide zone, tetrahedrite has nearly disappeared, stibnite, jamesonite, and, in the deepest levels, cylindrite taking its place. At present, there are six mills treating this ore, two at Potosi, two at Chocaya, one at Poopo, and one at Machacamarca. The ore is crushed dry, given a chloridizing roast, leached with water and hyposulfite solution (or with brine) to extract gold, silver and copper, and concentrated for tin with or' without regrinding.

Jan 8, 1920

By S. Usui, I. Iwasaki

The effect of pH on the adsorption of dodecylamine at the mercury-aqueous solution interface was investigated by differential capacity and electrocapillary measurements. With dodecylammonium acetate, the differential capacity curves showed two desorption peaks in the cathodic branch with their relative intensities varying with the solution pH. With dodecyltrimethylammonium chloride, only one cathodic de-sorption peak was observed in the same pH range. Through thermodynamic analysis of the electrocapillary curves, the adsorption density of undissociated amine was evaluated separately from that of aminium ion. The adsorption densities of the un-dissociated amine and of the total amine increased with increasing pH. The ratio at the interface of undissociated amine to aminium ion was several orders of magnitude greater than the ratio in the solution and increased with increasing pH. The potential at the closest distance of approach of counter ions to the mercury surface was compared with values of zeta potential on quartz previously reported. The most important variable in the flotation separation of minerals is probably the pH of the pulp, and a number of theories have been proposed to explain its effect on the condition of the mineral surfaces, on the dissociation of collectors and of inorganic and organic species (accidentally present or intentionally added) in the pulp, and on the mineral-collector interaction. In the development of a theoretical background for oxide flotation systems, an experimental approach based on electrokinetic measurements has been of much value, although the effect of pH becomes confounded since it governs both the electrochemical conditions of the oxide surface and the dissociation of the collector. For investigation of the adsorption behavior of long-chain collectors on oxide minerals, however, electrokinetic potential measurements are the most widely used technique. Hydrogen and hydroxyl ions are found to be the potential determining species, thereby governing the interfacial electrical conditions. The electrostatic interaction between the charged mineral surfaces and ionized collectors is regarded as the driving force for the adsorption of the collectors. An association of alkylamine collectors adsorbed on quartz surfaces has been postulated from streaming potential measurements, and a term "hemi-micelles" has been proposed.' The possibilities of coad-sorption of undissociated amine along with aminium ion has been inferred from contact angle measurements? and from adsorption studies.~ Electrochemical titration as applied to silver sulfide provides a more quantitative approach to the analysis of the electrical double layer at an ionic solid-solution interfaceqG and the electrochemical evidence for the adsorption of amine at pH 4.7 indicates a specific affinity of dodecylammonium ion towards silver sulfide surfaces, whereas at pH 9.2 the adsorbed species might be free arnine." A combination of differential capacity and electrocapillary measurements on a dropping mercury electrode was reported to be a sensitive method of provid- ing reliable information on the adsorption behavior of dodecylammonium acetate (DAA) at a natural (near neutral) pH.? It was also shown that there were striking similarities in the properties of the double layer and in the adsorption behavior of the amine on mercury and on such ionic solids as quartz, silver sulfide, and silver iodide. The effect of pH on the differential capacity curves at a mercury-sodium fluoride solution interface has been investigated by Austin and Parsonss who reported that between pH 7 and pH 11 there was very little effect. In the present paper, the adsorption behavior of DAA was investigated as a function of pH through differential capacity and electrocapillary measurements and the information gathered was correlated with that available in literature on quartz and silver sulfide. Experimental The apparatus and the method used for determining the differential capacity and the electrocapillary curves were identical to those described previously.' The ionic strength of the supporting electrolyte was fixed at 0.1 M with potassium fluoride, and the pH of the solution with potassium hydroxide. Only the neutral to alkaline range was covered in order to avoid the dissolution of the glass vessel with hydrofluoric acid. Results In Fig. 1 the differential capacity has been plotted against the applied potential at a DAA concentration of 10-' M at three different pH values. The curves are characterized by one capacity peak in the anodic branch, by two capacity peaks in the cathodic branch, and by a marked depression in capacity between the peaks. The depression indicates an adsorption of the arnine in this potential range. One of the cathodic peaks appears at pH 7.3 near -1.4 v and decreases with increasing pH. The other appears at pH 8.9 near —1.2 v and increases with increasing pH. At pH 9.6 only the latter peak is observed. Beyond the cathodic peaks, all the curves tend to converge with the curve in the absence of DAA, implying that two different species are being desorbed in this potential region. The anodic peak near 0.0 v increases markedly with increasing pH. The well-defined anodic peaks at pH 8.9 and 9.6 were accompanied by an appreciable increase in the current flow (in excess of O.luA), and, therefore, is a "pseudo-capacity"'" due to a

Jan 1, 1971

By R. J. Burgess, A. R. Ramey, A. R. Adams

During interpretation of pressure buildup tests on gas wells in a tight dolomite gas reservoir, peculiar behavior was noticed. Two straight lines were apparent. Effective permeability to gas taken from either straight line was about the same, and the Miller-Dyes-Hutchinson dimensionless time check for the straight line was proper for both straight lines. Geological data indicated the likelihood of scattered trending fractures in the reservoirs. Since the first straight Iine yielded permeability values close to the geometric mean permeability from core analyses, it was postulated that the reservoir model was that of an acidized well completed in the tight dolomite, but that widely scattered hairline fractures caused the mean permeability of the reservoir distant from the well to be higher than the matrix permeability. Because all other studies of fractured reservoirs to the authors' knowledge assumed that the fracture matrix was dense enough to communicate directly with the well, no interpretative methods were available. The Hurst line-source solution for a radial change in permeability for interference between oil reservoirs was adapted to pressure buildup testing. The result indicated that the first straight line should yield the proper matrix permeability and wellbore skin effect. The second straight line may be extrapolated to obtain static pressure. The time of bend between the straight lines was used to estimate distance to a fracture. Application to field test data is shown. It is believed that the methods developed and the case history presented will add to present tools available for pressure buildup interpretation. Introduction Since the pioneer studies by Miller, Dyes, and Hutchin-son1 and Horner' in 1950 and 1951, well test analysis has become recognized as one of the most powerful tools available to both production and reservoir engineers. Well test analysis serves as a logical basis for well stimulation and completion analysis, and for long-term reservoir engineering. Since the early 19501s, much effort has been placed on the development of well-test analytical methods. Reservoir and well conditions of increasing complexity have been considered systematically to provide the analyst with a catalog of causes and effects. Matthews and Russella state that some 200 papers dealing with this subject have been published in the last 35 years. Developments in well test analysis appear to have originated in one of two ways. Either a physically realistic field condition was anticipated and analytical solutions for the condition achieved, or anomalous field test behavior was recognized and interpretative methods sought for the anomaly. In recent years, it has appeared that the latter has inspired an increasing number of studies. The analyst today finds an increasing number of known cause and effect studies available for well test analysis, the classic of which is that of finding the specific flow problem that generated the answer — the well behavior. Although it may be impossible to achieve this goal uniquely, the analyst often is able to select a useful interpretation that combines all known performance and geologic data — or to show that various logical alternatives would not significantly affect the interpretation. During a recent reservoir study, we observed gas well test behavior that did not appear to fit behavior described previously. Although it cannot be said that we have found a unique interpretation, we shall present in this paper the peculiar behavior observed, and describe the reservoir and interpretative methods developed. Reservoir Description The subject gas reservoir is a 9-mile-long, narrow dolomite reservoir lying within a limestone of Ordovician age. (See Fig. 1.) The dolomitized rock in the field consists of dark brown to buff, dense to coarsely crystalline, vugular dolomite containing numerous hairline fractures, many of which may have been closed in the reservoir and parted when cores were brought to the surface. Larger fractures are also apparent in core, but usually are filled and sealed with euhedral dolomite crystals. Portions of the north flank of the reservoir are known to be cut by a sealing fault downthrown to the north. Gas wells located near the fault have higher open flow potentials than those more distant from the fault. This is believed to be a result of higher permeability near the fault due to more extensive and open fractures. Detailed coring and core analysis have been performed on several of the wells in this reservoir. Fig. 2 presents permeability variation' plots for both horizontal and vertical

Jan 1, 1969

By John Vasey

A shaft of 1690 m depth is currently being sunk to exploit a large copper sulphide orebody. The primary crusher chamber, main pump chamber and the other excavations on the crusher level were developed from the shaft during the sinking operation. The maximum principal stress is horizontal and has a magnitude twice that of the vertical stress. It increased linearly with depth and on the elevation of the crusher level, 1613 m below surface, the stresses induced by mining can exceed the strength of the rock. The development of a workable crusher level layout, and a crusher chamber design and support system are described. Excavation and support of the workings are detailed and a comparison of expected and actual results is made.

Jan 1, 1983

By W. P. Sykes

SEVEN years ago, Dr. S. L. Hoyt1 presented a masterful discussion of the hard metal carbides and cemented tungsten carbide. His lecture summarized most of the data then available in the field; many of the details relating to the production, properties and structure of cemented tungsten carbide had never been previously published, for, in fact, this information was only then being acquired. During the intervening years, the cemented carbides have assumed a place of real importance in the commercial field, with an ever widening variety of applications due to constant improvement in the control of production technique and the unremitting search for new compositions that might better the performance of the alloys in one or another type of service. The most recent summary of production methods, properties and guides for the successful application of the cemented carbides appears in the 1936 edition of the Metals Handbook. Of necessity, much detailed information relating to structures and physical properties is not included in such a summary, and it is with such details that the present discussion is concerned. STEPS IN PREPARATION While the past 25 years have contributed a valuable store of working knowledge in the field of powder metallurgy, many of the process controls are derived entirely from experience and are not as yet finally explained by a specific physical or chemical phenomenon. For most of the cemented carbides such difficulties are aggravated by our lack of knowledge not only of the complex alloy systems involved, but also by the possible changes in structure and even in composition which may accompany variations in temperature, heating time, and furnace atmospheres. The principal steps in the preparation of these cemented carbide alloys are fairly well known, but to supply a foundation for discussion these steps are briefly outlined as follows: 1. Formation of the metal carbide in the form of powder by heating a mixture of carbon and the metal powder or oxide for several

Jan 1, 1938

By Walter H. Ortel, George B. Wallace

INTRODUCTION A greater understanding is required about the factors which control tunneling operations if we are to meet the expected demand for tunnels. Much of the needed information can best be achieved by the proper use of instrumentation and advanced engineering concepts. Tunnel measurements and their analysis may prove to be the key which will give the insight necessary to understand the relationship of rock, tunnel supports, and linings. There are three main areas which can be improved through the use of tunnel instrumentation. First, and of prime importance, is safety for men and the project. When unstable conditions occur, sets become distorted. Even without measurements, it is sometimes possible to tell when trouble is approaching. In effect, the set acts as a load cell. Distortions in the set indicate reinforcements may be required to maintain stability. Additional sets or rock bolts, if they are placed soon enough, may provide this stability. However, when large rock displacements occur in short periods of time, it could be too late. Figure 1 is an example of the difficulties encountered in stopping moving rock. To stop the movement and possible failure, large props were placed above the spring line and the massive concrete gravity buttress was constructed along the legs. Rock bolts from the buttress deep into the rock were also used in an attempt to stabilize the rock mass. However, this work is for a highway tunnel and eventually these props and buttresses must be removed.

Jan 1, 1971

By Charles W. Goodale

The ores of the Butte district present a variety of combinations, and their treatment by concentration is an interesting study. They may be classified in general as follows: 1. Copper-silver ores, which are produced by the mines of the Anaconda group, and by the Mountain View, Colusa, Silver Bow and Parrot. The high-grade ores from these properties are roasted and then smelted; but a large proportion of the output is low-grade and siliceous, and hence requires concentration. The copper-bearing minerals are chalcocite, bornite, enargite and chalcopyrite, in varying proportions in the different mines, the gangue, which breaks readily into grains, being quartz and feldspar. 2. Silver-copper ores, of which the Gagnon vein is the largest producer. The grade of the ores from this mine is such that nine-tenths of the output requires concentration. The silver- and copper-bearing minerals of this vein are massive wurtzite, sphalerite, bornite, chalcopyrite, pyrite, tetrahedrite, enargite, tennantite and galenite, with a quartz gangue associated with feldspar and small quantities of barite and fluorite. The gangue is very hard and not at all granular. 3. Silver-ores containing a small amount of gold, embracing the product of the Alice, Magna Charta and Moulton claims, on what is known as the Rainbow lode, and that of the Lexington, Blue Bird, Nettie, Burlington and other mines. The gangue is quartz, carrying pyrite, sphalerite, galenite, tetrahedrite and argentite, with manganese in the form of rhodochrosite and rhodonite. Good results on ores of this class cannot be obtained by concentration, because large percentages of the silver-bearing minerals are disseminated through the gangue in such minute grains that even the finest practicable crushing

Jan 1, 1897

By P. F. Gnirk, J. B. Cheatham

The results of combined analytical and experimental studies involving simulated multiple bit-tooth penetration into mck are incorporated into a drilling rate equation for roller-cone bits assuming rather idealized downhole conditions. In particular, it is assumed that the rock behaves statically in a ductile fashion during bit-tooth penetration and that the rock chips are instantaneously removed from the bottom of the drill hole. The general analysis demonstrates an application of plasticity theory for the rock/bit-tooth interaction to the formulation of an upper limit on rotary drilling rate. INTRODUCTION Extensive experimentation involving single and indexed bit-tooth penetration into rock in a confining pressure environment has demonstrated that the chip formation process is of a ductile, or pseudoplastic, nature at sufficiently low differential pressures so as to be of interest in rotary drilling. Coincident with the experimentation, analytical consideration has been given to the theoretical problems of single and indexed bit-tooth penetration into rock. In general, the analyses have assumed that the rock behaves statically in a rigid-plastic fashion and obeys the Mohr-Coulomb yield criterion. The quantitative comparison between experimental and calculated values of bit-tooth load required for chip formation has been remarkably good for a variety of rocks commonly encountered in drilling and at simulated differential pressures as low as 500 to 1,000 psi. Results obtained recently for indexed bit-tooth penetration indicate that the work (or energy) required to produce a unit volume of rock chip can be minimized by a proper combination of bit-tooth spacing and bit-tooth load for a given rock type and differential pressure. By utilizing this information, it is possible to formulate a drilling rate equation, at least in a preliminary fashion, for a roller-cone bit performing under rather idealized downhole conditions. In particular, through the use of characteristic dimensionless quantities pertinent to a roller-cone bit and to indexed bit-tooth penetration, interrelationships among bit weight, rotary speed, rotary power, bit diameter, rock strength and bit-tooth shape and spacing can be explicitly expressed. In the formulation of the equations, however, it is assumed that the rock chips are instantaneously removed from the bottom of the drill hole and- that the rock behaves in a ductile manner during bit-tooth penetration. In addition, the effects of bit-tooth load application and penetration by a yawed tooth at an oblique angle are neglected. Although the analysis is presented in the light of some rather restrictive conditions, it does demonstrate a method of applying fundamental rock/bit-tooth interaction data, obtained by combining the results of analysis and experiment to the formulation of a drilling rate equation for rotary drilling. JNDEXED BIT-TOOTH/ROCK INTERACTION PREVIOUS RESULTS The mechanics of bit-tooth/rock interaction under simulated conditions of borehole environment have been extensively described in a number of papers.l-ll In particular, the effects of differential pressure, mechanical properties of rock, pore fluid, bit-tooth shape and spacing, rate of bit-tooth load application and dynamic filtration below the bit-tooth have been investigated experimentally. From a sequence of experiments.1-4 it was demonstrated that, for dry rock at atmospheric pore pressure, the mode of chip formation exhibits a transition, with increasing confining pressure, from predominantly brittle to predominantly ductile. This transition

Jan 1, 1970

By M. E. Fine, A. A. Henderson

Investigation of the tensile properties of silver based aluminum alloy crystals was undertaken because it appeared attractive for studying strengthening effects due to Suzuki locking with minimum complication. Yield drops were observed in all alloy crystals (1, 2. 3. 4, and 6 at. pct Al) after strain aging at room temperature. No yield drops were found in similarly grown and tested silver crystals. The yield effects are attributed to Suzuki locking but the major portion of the solid solution strengthening to other mechanisms. INVESTIGATION of the tensile properties of single crystds of silver alloyed with aluminum was undertaken because it appeared to be a system in which segregation at stacking faults associated with partial dislocations1 would be the dominant factor in anchoring dislocations. First, silver and aluminum have closely similar atomic sizes and thus solute atom locking of a dislocation due to elastic interactions should be unimportant. Second, while both X-ray2 and thermodynamic3 investigations show short-range ordering in silver-based aluminum alloys, the degree of local order is quite small (X-ray measurements give v = EAB - 1/2(EAA + EBB) = - 0.025 ev and thermodynamic measurements give v r -0.007 ev) and should not be important in strengthening dilute alloys. Third, the stacking fault energy of silver is probably low (as indicated by the profusity of annealing twins) and is very likely diminished further and quite rapidly by aluminum additions since the A1-Ag phase diagram shows a stable hexagonal phase at only 25 at. pct Al. Also, a careful investigation in this laboratory4 has shown that the ratio of twin to normal grain boundaries in recrystallized alloys increases with aluminum content. Thus, with minimum complication from other factors, Ag-A1 alloys seem attractive for studying strengthening effects due to segregation at stacking faults of extended dislocations. EXPERIMENTAL METHOD Single crystals measuring 250 by 5 by 1.5 mm of pure Ag (99.99 pct) and Ag-A1 alloys (A1 of 99.999 pct purity) of nominal compositions* 1, 2, 3, 4, and 6 at. pct were grown in high-purity graphite molds from the melt under a dynamic vacuum (1 x l0-5 mm Hg). The technique consisted of moving a furnace having a hot zone (which melted about 0.5 cm of alloy) over a horizontal, evacuated quartz tube con- taining the mold and alloy at a rate of 3/8 in. per hr. Chemical analysis showed roughly the first inch of the crystal to be solute poor, the last inch solute rich; and the center section uniform in composition within the sensitivity of the analytical method (± 0.2 at. pct Al). The center section of the crystal was cut into five specimens. Gage lengths of reduced cross section, measuring from 1.5 to 2 cm in length, were mechanically introduced by means of jeweler&apos;s files and fine abrasive cloth with the crystal firmly held in polished steel guides. One-third of the cross section was then removed by etching and electro-polishing, the crystals were all subsequently annealed for several days at 850°C in a dynamic vacuum (<1 x 10-5 mm Hg) and furnace cooled to 200°C. The crystal orientations were determined using the usual back-reflection Laue technique. The Laue spots were sharp and of the same size as the incident beam. However, microscopic examination showed the crystals to contain substructures with subgrains of the order of a micron in diameter. The details of this substructure are presently under investigation. Tensile testing was done with a table model Instron using a cross-head speed of 0.002 in. per min. For testing at various temperatures the following media were used: 1) 415oK, hot ethylene glycol; 2) 296ºK, air, acetone, water; 3) 273ºK, ice water; 4) 258ºK, ethylene glycol "ice" in ethylene glycol; 5) 200°K, dry ice in acetone; 6) 77ºK, liquid nitrogen. EXPERIMENTAL RESULTS A) Yield Behavior—A portion of an interrupted stress-strain curve for a 6 at. pct A1 crystal of the indicated orientation tested at room temperature is shown in Fig. 1. Initially, at (a), there is a small, gradual yield drop of about 10 mg per sq mm2. However, on stopping the test, and aging for a few minutes at (b), a sharp yield drop is found. Aging for longer times at (c) and (dl results in larger yield drops (and larger AT&apos;S). At, defined in Fig. 1, is usually larger than the yield drop by about 20 pct; however, this increase in the lower yield is transient since extrapolations of the flow stress curves join as may be seen from Fig. 1. (Both Laue and low-angle scattering photographs revealed no evidence of precipitation in a strain-aged 6 at. pct A1 crystal.)

Jan 1, 1962

By Paul D. Foote

Most of the treatises on metallurgy intimate that simultaneously with the development by the atomic physicist of a really satisfactory theory of the atom will be inaugurated a new epoch in the science of metals. Metallurgically and metaphorically, we shall dwell in the Utopia of Sir Thomas More. It is my privilege this afternoon to demonstrate that this state has not arrived. An atom is a miniature planetary system consisting of a positively charged nuclear sun about which revolve electrons each carrying the negative charge e. The charge on the nucleus is + Ze where Z is the atomic number and the number of planetary electrons in a neutral atom is equal to Z. These electrons are arranged in several groups having different binding energies. Ordinary x-ray phenomena relate to processes occurring deep within the atom, usually with electrons in the so-called K or L shells. Such electrons in the heavier atoms are so closely bound to the nucleus that the forces exerted by neighboring atoms in a solid are relatively inappreciable. For most practical x-ray investigation, the atom may be considered as in the gaseous phase completely isolated from its neighbors. The K radiation from an element in the gaseous state, in the solid or liquid phase, or even in combination with other elements in all its possible valences, is almost identical.‡ Visual and ultraviolet spectroscopy is concerned with disturbances of the most loosely bound outer or valence electrons of the atom, always in the vapor state. The remarkable progress of the last year in both theo-

Jan 1, 1926

By A. B. Kinzel

INCLUSIONS of nonmetallic matter have long been recognized as objectionable in steel. A complete theory of the effect of inclusions, which is consistent with that held today, was outlined in Howe&apos;s early work on the metallurgy of iron and steel. This, by analogy with wrought iron, assumes that the observed difference in properties between specimens with and across the direction of rolling is due to slag enclosures. The fact that wrought iron shatters in ballistic test is taken as an indica-tion of the effect of inclusions on the resistance to shock. Since that time, the development of the metallurgical microscope has shown the discrete nonmetallic inclusions in the iron matrix. Better resolution has, brought out the great number of inclusions, and the availability of good microscopes in steel mills and laboratories has constantly drawn more attention to these inclusions. This recent emphasis on inclusions has resulted in studies as to their nature, mode of formation and methods of elimination, such as the work of Wohrman, Dickenson, Herty, and Schenk. In addition to the published works; many investigations which have not been published&apos; have been carried out by private laboratories and have resulted in the application of specifications intended to limit inclusions in many qualities of steel. Nevertheless, a clear understanding of the quantitative effect of inclusions on the physical properties of steel has been lacking. It is the specific purpose of this study to determine the quantitative effect of inclusions on the physical properties of steel that determine its behavior under dynamic stress. The study has shown that a quantitative relation between counted inclusions and impact strength does exist in normalized steels, but &apos;that factors other than readily visible inclusions are equally important. Furthermore, the present commercial rating of inclusions is unreliable with respect to counted inclusions or dynamic tests, and this study indicates that the tensile-impact test is more reliable as a measure of quality.

Jan 1, 1931

By Arvid E. Anderson, Frank K. Cameron

The weathering of copper-bearing ores with the formation of a water soluble salt and the recovery of the metal by leaching and evaporation precipitation, are processes long known, which have at various times been utilized with more or less commercial success. It is commonly assumed that the technical principles involved are quite simple and their application to a particular case easy. If these assumptions were true, we should anticipate a long list of uniformly successful leaching operations, which is not the case, and one would be justified only in calling attention to either unique or peculiar features of any particular enterprise; whereas, in studying the problems of the recovery of copper from the old workings of the Ohio Copper Co. in the light of available descriptions of other leaching projects, we have not found the assistance hoped for to guide us to the best realization of our own opportunities. It appears desirable, therefore, to call attention to these guiding principles, together with a description of the facts of accomplishment. Justification lies in the fact that the leaching and precipitation of copper at the Ohio Copper Co. mine in Bingham Canyon, Utah, is successful. This success is measured by an average monthly production of 600,000 Ib. of copper at an average operating cost, to date, of 3.85 cents per pound at the company&apos;s workings, or 6.32 cents per pound after paying shipping and smelter charges on the finished copper. A total of 17,076,099 Ib. of copper had been shipped to the smelter from the beginning of operations, August, 1922, to April 1, 1925. Probably these results can be bettered with further study and realization of the factors involved and the devising of methods of meeting them. It is now an assured fact that the enterprise will have a relatively long and continuously profitable life and that its reserves will not, nor cannot, be suddenly and permanently depleted. It is particularly noteworthy that the financing of this enterprise has been entirely from its earnings. The few hundred dollars necessary for the first experiments and production were obtained by the sale of used, and no longer needed, equipment from a mill belonging to the company; and all funds since required throughout the growth and development of the enterprise, from a few troughs with a production of 2000

Jan 1, 1926

By J. M. Callow

THe results obtained by pneumatic flotation throughout the country on all classes of ore, and the tonnage now being treated by this particular method, speak for themselves. Its advantages over the so-called agitation process are now established by facts and data from practicc. The comparative efficiency of a rapidly revolving paddle, as a means for aerating an ore pulp, and of a cyeloidal or turbine blower for the same purpose, would seem to be so obvious as to leave no room for discussion. Practitioners in this art are to be congratulated on the acquisition of the valuable literary contributions that have recently been made on the theory of flotation by Messrs. Ralston, Van Arsdale, Taggart and Beach, and others, and the very valuable and able articles by Messrs. Laist and Wiggin on "Flotation Concentration at Anaconda, Mont.," by Dr. Rudolf Gahl on the "History of Flotation at Inspiration," and by David Cole on "The Advent of Flotation in the Morenci District." It is not within the province of this article to attempt an answer to the various issues raised in regard to the theory, or to defend the one advanced by me a year ago. But since discussion usually benefits the profession, a reply will be made to some of the statements made by the last-named writers. CoMPABATIVE SENSITIVENESS AND ATTENDANCE Concerning the article, "Flotation Concentration at Anaconda, Mont.," by Laist and Wiggin, a little explanation is in order. It should be stated that, with the exception of about 24 days at the end of the testing period, the Callow experimental plant at Anaconda was not run under my direction. This perhaps accounts for some of the concIusions drawn on page 499 of the descriptive paper. The conclusion that the use of acid seems to be of considerable advantage, calls for some comment. While the tests conducted by the Anaconda Copper Co. do show acid to be of considerable benefit, this is a consequence of using acid sludge as a flotation agent. My belief has always been that the Anaconda

Jan 1, 1917

By J. F. Martin, J. E. Friedline, L. M. Melnick, G. E. Pellissier

A method has been developed for determining gases in steel in which the gases are extracted by vacuum fusion and analyzed by mass spectrometry. This method is especially applicable for determining small amounts of oxygen and nitrogen. The lower limit of detection for both oxygen and nitrogen is 0.0001 pct with an average deviation of about 0.0001 pct for oxygen and 0.00008 pct for nitrogen. Hydrogen analyses by this method are in good agreement with analyses by vacuum tin-fusion. A complete analysis of all gases extracted from a steel sample can be accomplished in 40 min. It has long been known that certain of the gaseous elements exert particular effects on the physical and mechanical properties of steel. With the recent advent of new experimental steelmaking practices it is now possible to obtain steels with extremely low contents of such elements as oxygen and nitrogen. Present methods for determining these two gases are of insufficient sensitivity as applied to steels made by these newer practices, and therefore a new technique was considered necessary. A review of the literature showed that the conventional vacuum-fusion method1 was the procedure most suitable for modification to obtain a sensitive method for determining the gaseous elements present in steel simultaneously. However, for trace amounts of gases it is impractical to increase the sample size because of the physical limitations of the apparatus and the increased degassing time which would be necessary. Also, when only one of the desired gases is present in trace amounts, quantitative separation by conventional vacuum fusion is almost impossible. Since small analytical mass spectrometers are now commercially available, it was decided to use this instrument in conjunction with conventional vacuum fusion for both qualitative examination and quantitative determinations of the gaseous elements in steel. This technique has already been used with success for the analysis of copper and lanthanum.2"4 APPARATUS A vacuum-fusion unit was first designed and built, Fig. 1. This unit was designed especially for the determination of small amounts of nitrogen and/or oxygen in steel since an acceptable method (vacuum tin-fusion)5 was already in use for the determination of hydrogen in steel. The vacuum system was con- structed of Pyrex glass throughout. Mercury check valves were used in place of stopcocks in the high-vacuum section of the system. Ferromagnetic samples are normally introduced into the vacuum system through a mercury lift. In case of a break in the lift, the mercury is prevented from entering the furnace by a self-locking, mercury safety check valve, Fig. 2. This check valve, developed at our laboratory, is a modified T/S ball-and-socket joint placed in the sample inlet system between the mercury and the furnace. A sudden entry of mercury or air pushes this valve into the closed position, completely blocking the top of the mercury lift. The check valve is held in the closed position by the vacuum of the apparatus. A separate entrance tube also was placed in the system, so that samples which would amalgamate with mercury, or which are nonmagnetic, could be introduced into the furnace. A slightly modified Guldner-Beach furnace is used in this system.8 The optical flat was connected to the system by a ground-glass joint to facilitate cleaning, a quartz delivery tube was substituted for Pyrex, and the crucible was used uncovered. Fusion takes place in a high-purity graphite crucible insulated by — 200-mesh high-purity graphite powder. The crucible set (crucible and funnel) is suspended in a quartz crucible. The furnace envelope and the sample inlet system are exhausted by 2 single-stage, mercury-diffusion pumps in series. The first of these is a high-speed pump, which will work only with a very low backing pressure. This pump is used to exhaust the gases from the furnace as rapidly as possible. The second mercury-diffusion pump is used as a backing pump for the first; the capacity of this pump is much lower. However, it will work efficiently against a back pressure of 3 mm of mercury. To assure positive pumping, a modified Naughton and Uhlig condenser7 is used. With the use of proper valving the second pump is also used as a circulation pump in the catalyst system.

Jan 1, 1959

By R. F. Mehl, C. S. Barrett, A. H. Geisler

THE complicated nature of the property changes that accompany age-hardening has made it necessary to reconsider and to elaborate the simple dispersion theory.1 It has been apparent for some time that more direct information is needed concerning the atomic mechanism of precipitation from solid solution if the theory of age-hardening is to be developed past a purely qualitative stage.‡ Fortunately, in recent years information has been developed which allows us to trace in detail the lattice changes accompanying the process of precipitation from solid solution. This information relates chiefly to the sequence of the several stages of lattice alteration by which the matrix lattice is transformed to the equilibrium precipitate lattice, and permits reasonable inferences to be drawn concerning the states of internal strain that accompany these stages. This information is most complete for the solid solution of copper in aluminum. The equilibrium precipitate is the ?&apos; phase," CuA12." This forms in plates, parallel to the {100} matrix planes. The atom pattern and atom spacing on the plane in ?&apos; lying parallel to this plane are roughly similar to those opposite it in the matrix.&apos; The formation of ?&apos;, however, is preceded by the formation of a transition lattice ?&apos;, which again lies parallel to the matrix {100} plane, but in this case the matching of atom pattern and spacing across the matrix-precipitate interface is nearly perfect; thus there is lattice coherency across the interface and the interface is a plane of separation in only a very limited sense.4-8 Particles of ?&apos; may be recognized microscopically and form a well-defined Widmanstätten figure.* The ?&apos; lattice is recognized by the occurrence of diffraction lines on powder photograms or of spots on Laue photograms which may be analyzed in the usual ways to determine the lattice type and the lattice spacings. Very recent research 6.7,1 has shown, however, that streaks occur on the Laue photogram at an earlier point in time during the aging process. These streaks have been attributed to a preferential clustering of copper atoms into small platelike elements of only a few atoms in thickness and a few hundred atoms in diameter, probably of the composition of "CuA12," which may be designated as Guinier-Preston zones or aggregates.1 It is difficult if not impossible to determine the lattice type and lattice spacing in these aggregates. It is possible1 that these aggregates are in fact merely ?&apos; in a high state of dispersion; the inclination to argue this is strong, as we shall see later. Never-

Jan 1, 1941

By Richard P. Rothwell

FIRES in mines are so serious in their consequences and of such frequent occurrence, that their causes and the means of extinguishing them are certainly questions of the greatest interest to a large part of the engineering profession. We have already, in this country, many mines which have been burning for years, and though our hard anthracite is so difficult to ignite that for a quarter of a century after it was first discovered it was not known how to burn it except with the aid of an artificial blast, yet most of the fires which have occurred underground have been in anthracite mines, and in the coal itself. The injury which these fires have caused to properties in various parts of the anthracite regions, and the cost of extinguishing them, would amount to many millions of dollars, and they have also occasioned the loss of many valuable lives. It is not surprising, therefore, that the subject has already attracted much attention, and the exercise of great ingenuity ; and the present communication is made less with the expectation of announcing anything new, than with the object of putting upon record the present state of our knowledge on this subject, or, in other words, of indicating how defective are the present means of combating underground conflagrations. (Causes of Mine Fires.-Even upon the surface, fire is a terrible foe to contend with, and there is probably no other which inspires such thorough and well-founded alarm. With what feelings, then, must we look upon this destructive element, when its field is in the narrow galleries of a mine, where the poisonous products of combustion, spreading in every direction, protect, in the most effectual manner, the fire itself from the attacks of extinguishers, while, if the face of attack be ventilated so as to enable them to approach the seat of the fire, the air current simply increases the extent and violence of the conflagration. Fires underground originate in as various ways as those on the surface, and it is scarcely necessary to say that, except in the rare cases where they are the result of design, they are invariably classed as " accidents," and most generally as " unavoidable accidents." In reality, by an intelligent understanding of their causes and with due precautions, they can almost always be prevented. Ignorance and

Jan 1, 1876

By William E. Greenawalt

Ever since electrolytic copper refining gave promise of success, about a half century ago, efforts have been made to apply the idea to the extraction of copper from its ores. The methods of attack have, usually, been to leach with a dilute acid and then to deposit electrolytically the copper from the resulting solution with the simultaneous regeneration of the solvent used in the process. Many efforts have been made, and many patents have been taken out, both in the United States and abroad, to give this idea practical application, but only within the past few years have the difficulties been surmounted. Leaching and electrolysis, as applied to copper ores, are among the most promising fields in modern metallurgy. New conditions are arising, which will bring the wet methods into prominence; while high freight rates and increasing cost of fuel will tend to limit smelting to highly favored localities. The possibilities offered by the installation of hydroelectric plants and the greatly enlarged range of power transmission will greatly widen the field of electrolytic methods. Electrolytic methods are ideally adapted to hydroelectric development, for the load is constant throughout the full twenty-four hours, and the cost of both installation and operation of hydroelectric plants is not appreciably greater when operating for twenty-four hours than when operating for eight or ten hours; whereas, in fuel-power generation, as also in smelting, the cost is more or less in proportion to the fuel and power used. Nevertheless, fuel-power generation presents advantages in electrolytic methods, as the power plant may be located in a favorable place while the leaching and electrolytic plants may be located at the mine. The ultimate possibilities of the wet methods have yet to be determined. The possibilities of smelting have been thoroughly worked out; there is no unsolved major problem in copper smelting, and it has practically reached the limit of its possibilities. It seems hardly probable that any future improvement, either of method or apparatus, will greatly

Jan 1, 1924

By William E. Harris

Time and experience have demonstrated that by means of the Waelz process zinc, lead, cadmium, arsenic, antimony, bismuth and tin can be volatilized satisfactorily. In this way difficult gold ores are being treated to allow for the recovery of the precious metal. Iron ore containing zinc is being treated to remove the zinc and recover the iron. In Germany, thallium is being recovered in commercial quantities from the zinc oxide fume; indium, germanium and gallium are also concentrated to a degree warranting recovery, even though these rare metals are only recognizable in the ore by means of the spectroscope. The physical, chemical or mineralogical condition of the raw material affects very little the applicability of the process. The name Waelz is derived from the German word Waelzen, meaning a "trundling motion," which very aptly describes the movement of the charge through the slowly rotating kiln. The recovery of zinc and lead by volatilization in a rotary kiln has its origin in a process patented in 1910 by Edward Dedolph, of British Columbia. The Dedolph patent was taken over by the Metallgesell-schaft of Frankfurt-on-Main, Germany, which in cooperation with the Griesheim-Elektron, now a part of a large industrial combine, introduced certain improvements (Ohlmer, Specketer patents), but without bringing the process to a state suitable for large-scale operations. The war temporarily stopped all work on the process, and it was not until after the war that the Krupp Grusonwerk, of Magdeburg-Buckau, Germany, quite independently of the Metallgesellschaft, instituted research work in this field of metallurgy, which in 1923 led to the Waelz process proper. The Krupp Grusonwerk and the Metallgesellschaft A.G. later on collaborated, and by their joint efforts further developed and perfected the Waelz process, which they are marketing together as "Waelz-Gemeinschaft." The process is capable of treating a varied type of material; for instance, oxidized and sulphide zinc ores, calamine (zinc carbonate ore) waste dumps, jig tailings, jig slimes, table concentrate slimes, brass ashes, zinc-bearing iron ores (where the iron sinter is the real objective and the zinc oxide a by-product), electrolytic-zinc leach residues, zinc muffle residues and works sweepings, lead-furnace slags, tin ores and slags, anti-

Jan 1, 1937