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By A. Gatti

A dispersion of AI2O3 was produced within chromium by the hydrogen reduction of a solid solution of Cr2U3-A1203. The yesulting powder. was compacted, extruded, and the material tested in tension at various temperatures and in creep at 1800°F. The material is ductile above 1200°F and is at least twice as strong as electrolytic chvomium at all temperatures. Its creep resistance, rupture strength, and ductility at 1800°F warrant further work to improve its Low -temperatutre properties. BECAUSE of its high melting point and excellent corrosion resistance, chromium has long been considered as a base for high-temperature alloys. Most chromium base alloys, however, are extremely brittle at low temperatures. Elements such as nickel and iron lower the melting point of chromium and thereby limit its high-temperature usefulness. Chromium-alumina materials made by othersl, 2 have shown good high-temperature creep resistance but poor ductility and thermal shock resistance. Pure ductile chromium3 is weak at high temperatures and reverts to a brittle state if exposed to nitrogenous atmospheres. In sintered aluminum powder (SAP)4 and internally oxidized alloys of silver, copper, and nickel, fine dispersions of oxide phases can control hardness, recrystallization, and yield stress. The possibility of formation of a ductile, high-strength material by precipitating dispersions of alumina in a chromium matrix appears worthy of investigation. MATERIAL Powder Production—Chromium oxide and alumina in amounts to produce a final alloy of Cr + 16 pct AI2O3 by weight were colloid milled, filtered, dried and high fired for 16 hr at 1600°C in air. The resulting solid solution of oxides was ball-milled to a fine powder and the chromium oxide reduced to chromium by heating in pure dry hydrogen for 64 hr at 1400°C. Final Materials Produced by Powder Metallurgy Techniques—-Chromium powder, containing a disper-sion of alumina, was pressed into 1 1/8-in. diam slugs at 25 tons per sq in. and sintered 16 hr at 1400° C in pure dry hydrogen. The sintered slugs were encased in a stainless steel can, 2 in. in diam, and extruded at 1200° C through a 1/2-in. die. The 16 to 1 extrusion ratio produced a final chromium-alumina rod 1/4 in. in diam about 30 in. long. Samples of the rod were plunge-ground to small rupture bars of 0.82-in. gage length with a 0.01-sq-in. cross section. RESULTS Microstructure Studies—Fig. 1 is the microstruc-ture of the material in the as-sintered condition while Fig. 2 is the microstructure of the material as-extruded. Comparison of the as-sintered and as-extruded micrographs show the redistribution and realignment of the alumina inclusions by the extrusion

Jan 1, 1961

By W. S. Stahmann, F. W. Bowdish

Previously published experimental data showing that both collectable and non-collectable sulfide films may be formed on chrysocolla were analysed, and chemical mechanisms were proposed for the formation of the films. A special technique was developed by which the quantity of sulfur adsorbed was determined for samples sulfidized under different conditions of pH and soluble sulfide concentration. The data on sulfur adsorption were used together with the expression for the equilibrium constant for the proposed reaction to indicate the validity of the chemical mechanism theory. A recent paper 1 about contact angle studies on chrysocolla reported the effects of pH value and sodium sulfide concentration during sulfidization upon the character of the surfaces produced. In each experiment the surface of a specimen of chrysocolla was prepared by grinding it with fine abrasive and washing it in tap water. The specimen was then placed in the sulfidizing solution for 10 min, rinsed in tap water, treated for 15 min in a solution containing 30 mg of potassium amyl xanthate per liter, rinsed in distilled water, and tested for air adhesion in a contact angle apparatus. The results, when plotted as in Fig. 1, showed an island representing conditions giving air adherent or collectable surfaces surrounded by conditions giving non-collectable surfaces. Particular interest may be attached to the region of non-collectability to the right of and above the island in Fig. 1, and to the boundry curve separating these two regions. It is apparent that at any pH from 4.0 to 6.0, where a collectable surface may be produced, a sufficient increase in the sulfide concentration results in a non-collectable surface. Thus it appears that too much soluble sulfide has a depressing effect upon the mineral, just as it has in sulfide flotation. This paper presents some speculations regarding the chemical mechanisms by which the collectable and non-collectable sulfide films may be formed and reports on a physical-chemical study intended to support these speculations. THEORETICAL CONSIDERATIONS The experimental results presented in the previous paper were analysed in several ways in an attempt to understand better the chemical mechanisms involved. For several points on the boundary to the right of the region of contact in Fig. 1, molar concentrations of H+, OH-, HS-, and S= ions, as well as various ion concentration products, were calculated. Following the reasoning of Wark and Cox, 2,3 no single kind of ions may be credited with causing depression of the surface because none of them have a constant con-

Jan 1, 1968

By B. C. H. Steele, C. B. Alcock

In choosing solid oxide electrolytes for use in the measurement of thermodynamic quantities at high temperatures, the two most important criteria are the values of the partial ionic and electronic conduc tizities. Measurements of these conducticities have been made for some Group IVA oxides and solid solutions of these oxides with CaO, Y2O3, and La2O3. The total conductivities as a function of temperature. oxygen partial pressure, and composition were determined, as well as the electromotive forces of cells in which the oxygen partial Pressures of the electrodes were between 10-7 and 10-29 atm at 1000°C. Additional factors that influence the experimental arrangements, such as the operating temperature, the appropviate cell atmosphere, and electrode kinetics, are also discussed. IT has long been recognized that galvanic cells incorporating solid electrolytes can possess many advantages for the measurement of high-temperature thermodynamic data. Unfortunately, the electrical-transport properties have only been established for a few solid electrolytes, although attempts have been made, and are still being made, to use such materials as porcelain' and magnesia.' Kuikkola and Wagner have discussed3 and demonstrated4 various applications of solid electrolytes, and, in particular, their work stimulated the electrochemical measurement of oxygen activities using cells incorporating the solid oxide electrolyte, Zr0.85Ca0.15O1.85 The excellent characteristics of this oxide electrolyte have been confirmed by the investigations of Kingery et al.5 (oxygen ion diffusion), Carter and Rhodes6 (zirconium and calcium ion diffusion), and Weissbart and Ruka7 (electronic transference number). However the observations of Peters and Mobius,8 later confirmed by Schmalzried,9 indicated that the electronic component of zirconia-based electrolytes could become significant at low oxygen chemical potentials. Under these conditions, thoria-based electrolytes have obvious advantages arising from their superior thermodynamic stability. It was known that certain thoria solid solutions possessed defect fluorite structures containing anionic vacancies (cf. Zro.85Cao.l50O1. 85), although data on their electrical properties were conflicting. Kiukkola and wagner4 concluded that thoria-based electrolytes exhibited appreciable electronic conductivity, whereas Peters and Mobius8 mentioned that the electronic conductivity only became important at high oxygen partial pressures, but gave no further details. In addition, both Kiukkola and wagner4 and Peters and Mann'" had determined the oxygen chemical potentials associated with the Fe-FeO, Co-COO, Ni-NiO, and Cu-Cu2O equilibria, and it was not known whether discrepancies in their results could be attributed to the different cell design, or the thoria-based electrolyte used by Peters and Mann. These uncertainties have been resolved during the present investigation into the measurement of low oxygen chemical potentials, and transport properties of the relevant oxide electrolytes are presented and discussed. Other experimental difficulties associated with low oxygen chemical potential measurements are also described, with particular reference to the Nb-O system. 1. THEORETICAL CONSIDERATIONS Oxide systems of potential use as solid electrolytes possess a large energy gap between the valence and conduction bands. Little is known about the defects present in these wide-gap metal oxides as a function of impurity content and deviations from stoichiom-etry, or the mechanisms by which electronic charges move in these solids. For these materials it is convenient to represent the measured conductivity as the the sum of three terms: where a, is the conductivity due to positive hole conduction (p type), and oe is the electronic conductivity due to electron conduction (n type). U there is a large concentration of ionic vacancies fixed by composition then the ionic contribution will not be a function of oxygen pressure. Although the possibility of a pressure-independent electronic component also cannot be ignored, it is likely that such a term would only become significant at very high temperatures, and in general the positive hole conduction will increase with increasing oxygen pressure, and the electron conduction will increase with decreasing oxygen pressure. It follows that the total conductivity is related to oxygen partial pressure as follows:

Jan 1, 1965

By G. R. Speich, L. Zwell, H. A. Wriedt

HORNBOGEN1 has recently shown that it is possible to measure the degree of segregation accompanying cellular precipitation in ferritic Fe-Zn alloys by measuring the lattice parameter of the ferrite phase within the cell. In extending this work to study a wider range of composition and to evaluate the free-energy change accompanying the growth of the cells, the lattice parameter and the boundary of the a! phase in Fe-Zn alloys were redetermined to check the earlier work of Schramm.2 This appeared to be necessary since the Fe-Zn diagram has been drastically revised since the work of Schramm. Stadelmaier and Bridgers3 have recently shown that, contrary to prior belief: the y iron field is closed and the a phase boundary extends to an a + T + L peritectic at 782°C where peritectic a contains 42 at, pet Zn. The phase T in equilibrium with the a solid solution has a composition near Fe3Zn10 and a cubic 081 type structure.' The alloys were prepared by two different methods. In the first method carbonyl iron powder (400 mesh, 99.8 pet pure) and high-purity zinc powder (200 mesh, 99.99 pet pure) were mixed in a ball mill and then pressed in a die at 40,000 psi pressure to make compacts with a diameter of 5/8 in. and a thickness of l/4 in. These were sealed in evacuated quartz capsules, gradually heated to 1100°C over a period of 1 week (3 days at 600°C) 3 days at 800°C, 1 day at (1100°C), and then quenched in iced brine. For the alloys containing 23.4 and 30.1 at. pet Zn, the final homogenization anneals were performed at 1000" and 850°C) respectively, to prevent melting. In the second method, alloys were prepared by saturating high-purity iron millings (0.001 in. thick, 99.9 pet pure) in zinc vapor. For each alloy the impregnation was conducted at a fixed vapor pressure of zinc and a fixed temperature between 750' and 800°C. When saturated, the millings were quenched in water. The compositions of the alloys prepared by both methods are shown in Table I. The lattice parameters of the ferritic solid solutions were determined by comparing the 26 values of their 310, peaks (using Co Ka) or of their 211 , peaks (using Cr Ka) with those of corresponding peaks for high-purity a iron. The 20 values were measured at room temperature with an X-ray dif-fractometer (G.E.-XRD5). By using a fiducial value of 2.8664Å for the lattice parameter of pure a iron at 25oC,5 the lattice parameters of the zinc-bearing

Jan 1, 1964

By Norman Ketzlach

ANGANESE today overshadows all strategic materials in our planning for national se-curity," according to a report issued recently by the American Manganese Producers Association. By far the greater part of the manganese ore used in the United States is imported. "We have enough manganese ore in the United States to last from one hundred to three hundred years and longer, but most of the deposits are undeveloped. As in the case of copper, lead, and zinc, manganese ore, both foreign and domestic are low grade. Manganese ores have to be concentrated and processed. After being processed, domestic ores are higher grade than foreign." Most of the manganese ore found in this country, however, is not amenable to concentration by ore-dressing methods. Manganese Products, Inc. has developed a sulphurous-sulphuric acid leaching process for the recovery of manganese from low-grade, intermediate manganese ores. By the term "intermediate manganese ores" is meant those ores in which the manganese in the form of manganese oxides is found to have two different valences, usually two and four, as is probable in Mn,O, or the ore may be a mixture of manganous and manganic oxides. "Intermediate" manganese siliceous ores are ores in which the silica is a constituent of the ore and is loosely linked to the manganese by water of crystallization. This process has been carried out with the type of manganese ore found in the Olympic Peninsula of western Washington; Clough, N. C.; and Lava Hot Springs, Idaho, as well as just recently with manganese ore from Las Vegas, Nev. As far as the manganese leaching process is concerned, these ores differ primarily in the form in which the manganese oxides occur. The tetravalent manganese, the manganese existing in the dioxide form, is soluble in a sulphurous acid solution. To dissolve the divalent manganese, sulphuric acid is required. To dissolve the type of ore found in Washington and North Carolina, a mixture of both sulphurous and sulphuric acid is used. Whereas to dissolve the type of manganese ore found in Idaho and also in Montana, sulphurous acid alone is sufficient. The Nevada manganese ore is of the same type as that found in Idaho as far as the leaching process is concerned. It has long been known that manganese ores, with the exception of rhodonite, which is a true manganese silicate ore, can be dissolved readily in sulphurous and sulphuric acids.' The removal of the impurities such as silica, iron, and alumina from the resulting solution is the step that has been difficult. The process worked out by Manganese Products has been carried through pilot-plant equipment. This process has also been extended to the production of ammonium sulphate. Leaching of Ore: The manganese ore, ground to —-65 mesh is leached with sulphurous acid and sul-

Jan 1, 1951

By Norman Ketzlach

ANGANESE today overshadows all strategic materials in our planning for national se-curity," according to a report issued recently by the American Manganese Producers Association. By far the greater part of the manganese ore used in the United States is imported. "We have enough manganese ore in the United States to last from one hundred to three hundred years and longer, but most of the deposits are undeveloped. As in the case of copper, lead, and zinc, manganese ore, both foreign and domestic are low grade. Manganese ores have to be concentrated and processed. After being processed, domestic ores are higher grade than foreign." Most of the manganese ore found in this country, however, is not amenable to concentration by ore-dressing methods. Manganese Products, Inc. has developed a sulphurous-sulphuric acid leaching process for the recovery of manganese from low-grade, intermediate manganese ores. By the term "intermediate manganese ores" is meant those ores in which the manganese in the form of manganese oxides is found to have two different valences, usually two and four, as is probable in Mn,O, or the ore may be a mixture of manganous and manganic oxides. "Intermediate" manganese siliceous ores are ores in which the silica is a constituent of the ore and is loosely linked to the manganese by water of crystallization. This process has been carried out with the type of manganese ore found in the Olympic Peninsula of western Washington; Clough, N. C.; and Lava Hot Springs, Idaho, as well as just recently with manganese ore from Las Vegas, Nev. As far as the manganese leaching process is concerned, these ores differ primarily in the form in which the manganese oxides occur. The tetravalent manganese, the manganese existing in the dioxide form, is soluble in a sulphurous acid solution. To dissolve the divalent manganese, sulphuric acid is required. To dissolve the type of ore found in Washington and North Carolina, a mixture of both sulphurous and sulphuric acid is used. Whereas to dissolve the type of manganese ore found in Idaho and also in Montana, sulphurous acid alone is sufficient. The Nevada manganese ore is of the same type as that found in Idaho as far as the leaching process is concerned. It has long been known that manganese ores, with the exception of rhodonite, which is a true manganese silicate ore, can be dissolved readily in sulphurous and sulphuric acids.' The removal of the impurities such as silica, iron, and alumina from the resulting solution is the step that has been difficult. The process worked out by Manganese Products has been carried through pilot-plant equipment. This process has also been extended to the production of ammonium sulphate. Leaching of Ore: The manganese ore, ground to —-65 mesh is leached with sulphurous acid and sul-

Jan 1, 1951

By J. L. Snoek

[ ] DISCUSSION J. L, SNOEK*-Stress-induced preferential diffusion in cubic body centered metals in the annealed state provides us with a powerful tool for determining the mobility of interstitially solved atoms as well as their location in the lattice and the exact nature of the distortion brought about in the lattice by their presence. Calculations given by D. Polder31 show that the distortion of the lattice, besides being proportional to the applied stress P, is also proportional to [VC, RT + xVCo] where T, V and Co are the temperature, molar volume of the solvent and molar concentration of the solute respectively and x is a constant describing the mutual interaction energy of the dissolved particles. This calculation obviously is no longer valid if x is negative and the abso¬lute value of xVCo surpasses that of RT. The lattice may then be expected to become tetragonal spontaneously. Such a spontaneous tetragonality seems to have been observed by W. Klemm and L, Grimm for the case of oxygen solved in vanadium.32 Measurements of the internal friction in cold worked iron containing carbon or nitrogen should provide us with information on the mobility as well as the preferential location of these particles in the iron lattice in the cold worked state. The work by T'ing-Sui Kê is a valuable contribution to this problem, The data obtained by T'ing Sui Kê and myself on cold worked samples of iron seem to indicate that carbon and nitrogen in these samples are found either in the normal (1/2 , 0, 0) interstices or in a new preferential position created by the cold working. The latter positions in my opinion can hardly by anything else but the edges of the dislocations. The observed larger distances of diffusion might be explained by assuming that the carbon atoms when freed from a certain dislocation by thermal agitation must diffuse over several atom distances before being caught in another dislocation. The theory however needs working out and no doubt will be much more complicated than the one valid for the annealed state. T'ING-SUI KÊ (author's reply)-It is highly encouraging to read the written discussion given by Dr, Snoek who initiated the theory of stress-induced preferential diffusion in cubic body centered metals in the annealed state, Since the presentation of this paper, the author has done more experimental work on this subject which seems to be able to settle several of the points raised by Dr. Snoek. It has been found that such stress-induced preferential diffusion occurs also in the solid solutions of carbon,33 oxygen,34 and nitrogen35 in tantalum which has a body centered cubic structure. Analysis of the shape of the observed internal friction. peaks indicates that the inter-

Jan 1, 1948

By G. D. Van Arsdale

THE paper of Mr. Posnjak presents a laboratory confirmation of the well known facts that air ox-idation of pure solutions of ferrous sulfate is slow and difficult and that, like many other similar reactions, the speed, may be greatly accelerated by the presence of other substances, often in very small amounts, the effect of the presence of copper being determined ex-perimentally in this case. However, it should not be. overlooked that copper is always present in heap leach-ing solutions in amounts equal to or greater than those in the experiments described; therefore the paper may be considered as an explanation of present results rather than a possible improve-ment to be added to present practice. It is not practicable and it does not pay to precipitate copper by ce-mentation below a point about 5 lb. per 1000 gal., equivalent to about 0.0005 mol. Cu. per liter, compar-ing with the approxi-mately 0.0009 mol. per liter of curve 2 in the diagrams given of course, also, in the heaps local concentrations are usually very much higher than this, which is also true of the effluent li-quors, so that I feel that it is safe to say that copper is already present in amount sufficient to realize, as large an accelerating effect as is practicable. Too much im-provement or refinement cannot be expected in a method of this kind, due to commercial limitations. It should be remembered that chemically and physically there is no sharp dividing line between leaching in place, heap leaching, and the usual tank leaching practice, practi-cally the same reagents being used in all three. From the viewpoint of extractions, etc., it is not common sense to apply leaching in place to an orebody carrying enough copper to pay for mining; and the same is true of heap leaching, for an ore carrying enough to pay for the crushing, handling, etc., of ordinary leaching. That is to say, leaching in place should properly be consid-ered only for an ore too low-grade to pay for mining, and heap leaching for the next higher grade, still how-ever too low-grade to pay for crushing and other re-finements. There is no advantage in leaching without mining or in heap leaching except lower cost of in-stallation and handling; on the other hand there are very distinct disadvantages which are inherent and which should prohibit their use except where necessity requires. The object of metallurgy is to make money out of the handling of ore, and it is purely a question of money as to how far we can go in "improving" or

Jan 7, 1927

By K. Tanaka, J. D. Mote, J. E. Dorn

It) an attempt to ulLcoce.lP the operative strain-rate-contl-olliy: dislocation nieclzanistns, specially oviented sizgle clystals of the intel-nzediate 1zexagonal phase containing Ag plus 33 at. pct A1 were tested in tension over a wide range of temperatures. Slip was observed to take place by the {0001} <1120> {l100} mechani fracture took place across the(i100) plane and winning occurred by the (i01Z) ?lechanisn. Basal slip exhibited a strong yield point over the -alzge from 77 to 450°K, the upper ,esolved shear st]-ess having the exceptionally high value of 10,500 psi over this entire ?-a?zge of tenzpei,atuves. The critical 9-esolved shear stress for prismatic slip decreased f7-om 48,000 psi at 4.3"K to 23,000 psi at 170°K (Region 1) follozcirg zt:lzich it decl>eased sloz&ly to 21,500 psi at 475°K (Res&apos;on II); from 475" to 575°K (Regioz III), the c7-itical esolced shear stress dec&apos;-eased precipitously to 2000 psi; and from 575" to 750°K (Region IV) it decreased less afi&apos;dly to a low value of about 500 psi. Pvistintic slip in Region I was pobably controlled by the tliel-nally activated riecharzisui of nucleation and g,-ozcth of kinks in dislocations lying in Peierls potential troughs. In Region II for prismatic slip the critical 1-esolved shear stress was slzocn to be deteemined by sh0l.t-range 01-dering, Overall the forgiorz fo basal slip, 7.c.lre1-e a Strong yield-point phenorlienu ia7as observed, the critical vesolved slzea?-stress was shoztn to be determined by n conibirzation 0-f Szizuki locking and short-range-order Izavderzizg, The precipitous decrease in the critical resolved shear stress with increase in ter,/pe7-atrir-e over Region HI was tentatively ascribed to a decrease in the degree of slort-)ange 07-del;iqq (0)- clusteing) and also the effect of fluctuations the degree of o?der, It is at pgreser2t zrtzce)taitz as to 1t1hethe1- these or other possi1)le effects are also ,esponsible. fo- the data obsel-ved 172 Region IV. 1NTEREST in inter metallic compounds stems not only from their role in dispersion hardening of polyphase alloy ystems but equally from their potentialities for high strength, hardness, and stability not only at atmospheric temperatures but especially at elevated temperatures. As summarized in a re- cent symposium of the Electrochemical Society on "Mechanical Properties of Inter metallic Compound", most of the experimental evidence regarding the mechanical behavior of intermetallic compounds centers about the effect of temperature on the hardness and ductility of polycrystalline specimens. The available data reveal that the plastic behavior of intermetallic compounds might be rationalized in terms of the usual dislocation mechanisms appropriate to a solid solutions providing the additional complexities arising from crystal structure, long-range ordering, short-range ordering, and defect lattices are taken into consideration. It is apparent, however, in terms of the history on a solid solutions, that a complete detailed mechanistic rationalization of dislocation processes may not be possible until the deformation processes are studied in single crystals of intermetallic compounds. The present paper contains a preliminary report on the plastic behavior of single crystals of the hexagonal Ag-A1 intermetallic phase over a wide range of temperatures. The results confirm the thesis that single crystal data provide a most effective method of identifying operative dislocation mechanisms in intermetallic compounds. EXPERIMENTAL TECHNIQUES Several factors prompted the selection of the hexagonal Ag-A1 intermetallic phase for this preliminar investigation on the plastic properties of single crystals of intermetallic compounds: 1) This phase has a wide solubility range5 which would permit future investigations on the effect of composition and axial ratios on slip mechanisms. 2) Although it undoubtedly exhibits short-range ordering (or clustering) this intermetallic phase is free from complexities arising from long-range ordering.6 3) Since the atomic radii of aluminum and silver are practically identical, the possible complications due to Cottrell locking are minimized. 4)Whereas the dislocations on the basal planes are expected to dissociate into Shockley partials and are thus susceptible to Suzuki locking, those on the prismatic planes probably remain complete. 5) The axial ratio, being 1.61, is almost ideal, suggesting that short-range ordering may be almost spherically symmetrical. The present investigation was conducted exclusively with the hexagonal Ag-A1 alloy containing 33 at. pct Al. Preliminary investigations revealed that this alloy undergoes basal slip by the (0001)

Jan 1, 1962

By W. A. Bruce

This paper covers the theory and present state of development of an apparatus for the nonmathematical analysis of complex problems of reservoir and well behavior. At the present stage of development of this apparatus, it is capable of solving the water-drive problem of any reservoir performance for which a mathematical solution has been presented in the literature, either on the basis of steady or unsteady-state flow analysis. The theory is presented for the extension of the scope of this analyzer along the lines of the present development. The resulting apparatus should be able to solve reservoir-performance problems previously thought too difficult for practical solution by mathematical means. As an illustration of its operation and present scope, the analysis of a reservoir problem and synthesis of expected performance is presented. Introduction In this method† of analyzing problems of petroleum-reservoir and well behavior, the porous continuum of the reservoir is assumed to be divided into small blocks, or units. Each block is assumed to be small enough so that for a material balance on the fluids in the block an average pressure for the block can be used. In analyzing reservoir behavior from this point of view by mathematical means, a set of simultaneous difference equations would be obtained (two for each block), which must be solved or combined into a partial differential equation. In the method to be described here, instead of solving these sets of equations analytically, electrical units are constructed, which will behave in respect to the flow of electricity exactly as the reservoir units behave under various conditions of fluid flow. The electrical units are then wired together in the same way that the reservoir units are connected naturally by virtue of their geometrical locations and shapes. Fluid-Flow Equations Consider a block in a reservoir. Assume that reservoir fluid (or fluids) is flowing in at one face and out at the opposite face, and that the block is small enough so that at all points the stream lines are within one degree of perpendicular to the face. Furthermore, assume that the pressure, pi, at the upstream face (Fig, I) is not more than one per cent greater than P2 the pressure at the downstream face. A material balance will show that the mass of fluid flowing out less the mass of fluid flowing in will equal the change in density times the fluid volume. This is expressed in the equation:

Jan 1, 1943

By Nathan C. Rockwood

The title of this paper, I understand, was suggested by professional mining engineers as an opportunity for someone to pose problems rather than to offer solutions for them, but the paper will merely attempt to pose some of the production problems of the mineral aggregates industry in such manner as to create professional interest in their solution by the mining engineer, geologist, geochemist and the metallurgical engineer versed in mineral-dressing technique. Definition of Mineral Aggregates " Mineral aggregates" may be defined as fragments of any rock or mineral used to supply bulk or volume or substance for a given purpose. For example, mineral aggregates are used in portland-cement concrete to provide bulk with the expenditure of the least feasible amount of cement binder. Mineral aggregates are used without port-land cement or bituminous binder in highway and railway roadbeds to provide substance, to carry loads. provide aggregates are used in filters for water and sewage, to provide substance for the liquid to trickle through. These are only a few typical uses of mineral aggregates. For all these uses, strength, toughness, resistance to abrasion, and durability are usually prime requisites; so, while theeretically mineral aggregates may be of any mineral composition, what really is desired is a mineral composition as nearly inert under the conditions of use as anything of earthly origin can be. Exploration and Possibilities of Development The distribution of deposits of mineral aggregate is universal, since almost any part of the earth,s crust can be used; even the top soil is sometimes used in stabilized surfacing for highways or airport runways. Nevertheless there is ample opportunity for exercise of the talents of the mining engineer and the geologist in finding the particular deposit that will be most economical to develop, keeping in mind such considerations as: (i) quality and mineralogical characteristics of the material; (2) size and permanency of the market; (3) final cost of opening and development of the deposit; (4) selection of location of plant; (5) methods and costs of distribution of the product in comparison with both present and possible future competition; (6) selection of the proper type of operating equipment; (7) estimation of probable waste products and their disposal. These are typical but there are other considerations also. Because profit margins are far smaller than in any comparable mining operation, it is all the more logical to assume that a higher degree of expert knowledge is desirable to make a success of a mineral-aggregates business. The industry has much engilleering talent in its operating branch, but it lacks, to a considerable degree, engineering talent with experience

Jan 1, 1948

By W. A. Bruce

This paper covers the theory and present state of development of an apparatus for the nonmathematical analysis of complex problems of reservoir and well behavior. At the present stage of development of this apparatus, it is capable of solving the water-drive problem of any reservoir performance for which a mathematical solution has been presented in the literature, either on the basis of steady or unsteady-state flow analysis. The theory is presented for the extension of the scope of this analyzer along the lines of the present development. The resulting apparatus should be able to solve reservoir-performance problems previously thought too difficult for practical solution by mathematical means. As an illustration of its operation and present scope, the analysis of a reservoir problem and synthesis of expected performance is presented. Introduction In this method† of analyzing problems of petroleum-reservoir and well behavior, the porous continuum of the reservoir is assumed to be divided into small blocks, or units. Each block is assumed to be small enough so that for a material balance on the fluids in the block an average pressure for the block can be used. In analyzing reservoir behavior from this point of view by mathematical means, a set of simultaneous difference equations would be obtained (two for each block), which must be solved or combined into a partial differential equation. In the method to be described here, instead of solving these sets of equations analytically, electrical units are constructed, which will behave in respect to the flow of electricity exactly as the reservoir units behave under various conditions of fluid flow. The electrical units are then wired together in the same way that the reservoir units are connected naturally by virtue of their geometrical locations and shapes. Fluid-Flow Equations Consider a block in a reservoir. Assume that reservoir fluid (or fluids) is flowing in at one face and out at the opposite face, and that the block is small enough so that at all points the stream lines are within one degree of perpendicular to the face. Furthermore, assume that the pressure, pi, at the upstream face (Fig, I) is not more than one per cent greater than P2 the pressure at the downstream face. A material balance will show that the mass of fluid flowing out less the mass of fluid flowing in will equal the change in density times the fluid volume. This is expressed in the equation:

Jan 1, 1943

By Nathan C. Rockwood

The title of this paper, I understand, was suggested by professional mining engineers as an opportunity for someone to pose problems rather than to offer solutions for them, but the paper will merely attempt to pose some of the production problems of the mineral aggregates industry in such manner as to create professional interest in their solution by the mining engineer, geologist, geochemist and the metallurgical engineer versed in mineral-dressing technique. Definition of Mineral Aggregates " Mineral aggregates" may be defined as fragments of any rock or mineral used to supply bulk or volume or substance for a given purpose. For example, mineral aggregates are used in portland-cement concrete to provide bulk with the expenditure of the least feasible amount of cement binder. Mineral aggregates are used without port-land cement or bituminous binder in highway and railway roadbeds to provide substance, to carry loads. provide aggregates are used in filters for water and sewage, to provide substance for the liquid to trickle through. These are only a few typical uses of mineral aggregates. For all these uses, strength, toughness, resistance to abrasion, and durability are usually prime requisites; so, while theeretically mineral aggregates may be of any mineral composition, what really is desired is a mineral composition as nearly inert under the conditions of use as anything of earthly origin can be. Exploration and Possibilities of Development The distribution of deposits of mineral aggregate is universal, since almost any part of the earth,s crust can be used; even the top soil is sometimes used in stabilized surfacing for highways or airport runways. Nevertheless there is ample opportunity for exercise of the talents of the mining engineer and the geologist in finding the particular deposit that will be most economical to develop, keeping in mind such considerations as: (i) quality and mineralogical characteristics of the material; (2) size and permanency of the market; (3) final cost of opening and development of the deposit; (4) selection of location of plant; (5) methods and costs of distribution of the product in comparison with both present and possible future competition; (6) selection of the proper type of operating equipment; (7) estimation of probable waste products and their disposal. These are typical but there are other considerations also. Because profit margins are far smaller than in any comparable mining operation, it is all the more logical to assume that a higher degree of expert knowledge is desirable to make a success of a mineral-aggregates business. The industry has much engilleering talent in its operating branch, but it lacks, to a considerable degree, engineering talent with experience

Jan 1, 1948

By M. J. Mullikin, J. B. Conway

for use in describing combined first- and second-stage creep data. In the above ?o represents the instantaneous strain on loading, ?t the limit of transient creep, ?S the steady-state creep rate, t the time, and ? a constant leading to the exhaustion rate of transient creep. It was noted that this equation was similar in form to that proposed originally2 by McVetty. This type of equation was also suggested by Andrade and Aboav3 in studies of the shear strain of cadmium. Calculation of the constants ?o, ?t, ?, and ?s, in Eq. [ l] is somewhat involved due to the slight complexity of this relationship. In the paper by Garofalo a computer approach based on a least-squares analysis was recommended. Such an approach involves a trial and error solution but when a computer facility is available the difficulties in this calculation are of little consequence. It does mean however that the evaluation of this type of equation would become quite tedious if computer facilities were not available. Some recent studies have identified a fairly straightforward method for calculating the constants in the Garofalo equation. While not leading to a least-squares evaluation the approach is accurate and is recom-

Jan 1, 1967

By M. S. Seltzer

High temperature steady-state creep rates have been determined jor lead sulfide single crystals whose defect concentrations were fixed by equilibration under controlled sulfur pressure. The activation energy of creep, Qc , for undoped lead sulfide, is a function 01 composilion, decreasing from 2.9 to 2.2 ev as the carrier concentration increases from 9 x 1016 to 8 1018 electrons cm-3 for lead excess crystals, and increasing from 1.7 to 2.3 ev as the concentration of holes increases from 4 x 1017 to 1 x 1018 cm-3 in sulfur excess material. For five different composilions, Qc for undoped and bismuth-doped crystals has been found to be equal to Qpb + Qs, the self-diffusion activation energies for lead and sulfur in PbS. It is well-established1 that high-temperature steady-state creep of pure metals is a diffusion-controlled process, where the activation energy of creep is equal, within experimental error, to the activation energy of self-diffusion. The relationship between the activation energy for steady-state creep and those for self-diffusion in binary compounds is more complicated, however, because two different diffusing species must be considered, and becayse the activation energies may be influenced by compositional variations and by foreign atom additions.2-4 In some cases experimentally determined creep activation energies are correlated with those for self-diffusion of the slower-moving species, but such agreement is by no means universal. Interpretation of experimental results is difficult because few investigations include measurements of creep rates and self-diffusion coefficients of both diffusing species on single crystals of similar composition and foreign atom concentration. The objective of this investigation, therefore, is to determine the influence of stoichiometric defects and foreign atoms on steady-state creep and self-diffusion for a well-characterized binary compound. Lead sulfide, a compound semiconductor which crystallizes in the NaC1-type structure, and whose homogeneity range includes compositions on either side of the 1:l atom ratio, was chosen for study in this investigation. The pressure-temperature-composition relations for PbS are available,5,3 and deviations from stoichiometry may be monitored by electrical measurements.7 Single-crystal specimens are available to allow observation of effects due to bulk phenomena without interference from grain-boundary effects. These crystals have been employed to determine steady-state creep rates under compressive stress for "pure" and bismuth-doped PbS as a function of sulfur pressure and temperature as well as crystal orientation and applied stress in order to establish the relationships between defect concentrations and creep rates. EXPERIMENTAL PROCEDURES Crystal Growth. Lead sulfide crystals, prepared by the Bridgman method, are grown in evacuated quartz crucibles, filled with almost equal atomic proportions of high-purity (99.999 pct) lead and sulfur, and heated to a temperature above the melting point of PbS (about 1127°C) so that the lead and sulfur react to form molten PbS. The crucible and melt are dropped through the hot zone of the crystal-growing furnace at the rate of 1 cm per hr. The maximum melting point of PbS is slightly on the lead-rich side of the 50:50 composition; hence crystals grown from a near stoichiometric melt are usually n-type semiconductors containing excess lead atoms. Typically the lead excess concentration in solid solution with the PbS is 3 x 1018 atoms cm-3. Crystals containing either 1/20 or 1/2 mole pct Bi2S3 were prepared by addition of the foreign atoms prior to crystal synthesis. Preparation of Specimens of Controlled Stoichiom-etry. Since it is difficult to grow crystals of desired composition, the process of crystal growth and control of stoichiometry are separated into two distinct operations. Equilibration of as-grown PbS to a desired composition is most easily accomplished by first annealing the n-type crystals under high sulfur pressure (about 1 atm) at temperatures above 700°C. This process serves to put excess lead precipitates into solution, yielding 0 -type crystals upon quenching to room temperature. Inter diffusion occurs readily in crystals so treated, and the methods described by Bloem may then be employed to obtain crystals of controlled stoi-chiometry. For the creep measurements made in this study, this involves heating crystals in mixtures of H2 and H2S The equilibrium constant for H2S is given by: Thus the sulfur partial pressure is obtained from knowledge of the H2/H2S ratio and Kh2S for the temperature in question. Fig. 1 shows the p-T-x diagram for PbS. It can be seen that, within the stability limits for single-phase lead sulfide, desired compositions may be obtained by equilibrating under a specified sulfur pressure and temperature. Characterization of Crystals. The principal methods for evaluating PbS crystals include measurement of electrical properties and mass-spectrographic analysis. The measured electrical parameters include Hall coefficient, conductivity type, and electrical resistivity Bloem7 has shown that there is a 1:l relation between the defect concentration and carrier concentration obtained. Hence, if the contribution to the carrier con-

Jan 1, 1968

By K. R. Van Horn

RESIDUAL stresses in metals operate under a cloak of mystery, as they have neither been seen in the laboratory nor detected by means of the microscope. In spite of their phantom-like nature, they frequently exert metallurgical effects that cannot be ignored. In some cases the results have been detrimental, causing rejections or premature failures, but frequently the effects have been highly beneficial to the producer or consumer of metal products. First, however, what is a residual stress? When a metal is plastically deformed by bending, rolling, pressing, or by a phase transformation or precipitation from solid solution, or by a sharp temperature gradient resulting from nonuniform cooling, quenching, or welding, it remains in a state of strain. The strains or strain gradients produced by such operations and retained after all external forces are released are known as residual strains, and the accompanying stresses as internal or residual stresses. Many defects or failures in metal products have been ascribed to residual stresses, sometimes erroneously, because there was no other apparent explanation after the usual metallurgical tools of diagnosis had been applied. For example, during World War 11, the forged aluminum alloy aircraft cylinder head in the reciprocating engine began to replace the cast head with the familiar cooling fins. The fins were machined in the solid forged head by an ingenious milling operation. One plant reported an epidemic of excessive distortion during the delicate high-speed milling. A thorough examination revealed that the composition, heat treatment, mechanical properties, and metallurgical quality of these heads were comparable to those of forgings that machined satisfactorily. It was then claimed that the cause of the machining difficulties was connected with residual stresses resulting from the quenching during the solution heat treatment. An elaborate stress analysis actually demonstrated, however, that the magnitude of residual cooling stresses was lower in the cylinder heads which machined poorly than in those which were satisfactory in this respect. Subsequent tests proved that the machining problems in this case originated from variations in the tools and tool design. Sources of Residual Stresses in Metals Residual stresses are of two origins—mechanical and thermal. Thus, stresses may be produced in a metal by any cold-working process. The distribution and magnitude of these mechanically produced stresses can be calculated in a satisfactory, although approximate, manner for such simple cases as bending, torsion, and expanding of tubes. However, most manufacturing processes are too complex, and the original stress-strain relations in the products are not sufficiently known to permit calculation of the resulting residual stresses. Also, a specific process, such as wire drawing, may vary in complexity or uniformity of working, and large or small residual stresses may result, depending on the conformation of the dies and other features of the working process. Neither substantially unidirectional deformation, such as can be imparted by stretching a metal product having essentially the same mechanical properties throughout the cross section, nor deformation

Jan 1, 1954

By Frank R. Milliken, Robert Goodwin

In September 1937, the Ohio Copper Co. inaugurated the treatment of its copper-bearing mill tailings at Lark, Utah. These tailings had been accumulated during the regular operation of the Ohio Copper mine and mill over the period 1907 to 1919. Gravity concentration had been employed except for a comparatively short period in 1919, when flotation was used. The ore milled during that period assayed about I per cent Cu. The chief copper mineral, chalcocite, was disseminated in a shattered quartzite, mainly along fracture or cleavage planes. The quartzite gangue was extremely hard and grinding to liberation resulted in excessive sliming of the "sooty" chalcocite, with consequent high tailings losses. Recovery on the seven million tons treated was probably less than 60 per cent of the total copper content. As early as 1918, attempts had been made to sample the dump. In 1928, a complete sampling program was undertaken. The sampling consisted of seventy-four 5-in. post auger holes drilled to the full depth of the dump at regular intervals of 250 ft. Each 10-ft. portion thereof comprised a sample for analysis. Each sample was screened, rolled, divided into three parts, dried and assayed. The reject was retained for testing purposes. From the depth of the auger holes a contour map of the dump was plotted, Fig. I, which gives percentages of tonnage and copper content. The tonnage within the limit of the drill holes was estimated at about five million tons with an average content of 0.42 per cent Cu, 31 per cent of which (0.13 per cent) was acid-soluble. A screen analysis of the composite dump sample is shown in Table I. Flotation tests by several companies and individuals were then made, the results of which ranged from 62 to 74 per cent recovery. On the basis of these, a 200-ton pilot plant employing straight flotation was built and operated for a few months. Operation of this plant was unsuccessful, as no provision had been made to handle the copper-bearing solutions resulting from the water-soluble copper, a point that was overlooked in the laboratory test work. Attempts to decant the copper-bearing solution for precipitation in the usual manner ahead of flotation were not satisfactory because of low water recovery (owing to poor settling characteristics of the pulp) and contamination of the copper precipitate with unsettled slime. Low copper prices in 1931 necessitated the termination of testing. With the stimulus of higher copper prices in 1937, a review was made of metallurgical

Jan 1, 1943

By Robert Goodwin, Frank R. Milliken

In September 1937, the Ohio Copper Co. inaugurated the treatment of its copper-bearing mill tailings at Lark, Utah. These tailings had been accumulated during the regular operation of the Ohio Copper mine and mill over the period 1907 to 1919. Gravity concentration had been employed except for a comparatively short period in 1919, when flotation was used. The ore milled during that period assayed about I per cent Cu. The chief copper mineral, chalcocite, was disseminated in a shattered quartzite, mainly along fracture or cleavage planes. The quartzite gangue was extremely hard and grinding to liberation resulted in excessive sliming of the "sooty" chalcocite, with consequent high tailings losses. Recovery on the seven million tons treated was probably less than 60 per cent of the total copper content. As early as 1918, attempts had been made to sample the dump. In 1928, a complete sampling program was undertaken. The sampling consisted of seventy-four 5-in. post auger holes drilled to the full depth of the dump at regular intervals of 250 ft. Each 10-ft. portion thereof comprised a sample for analysis. Each sample was screened, rolled, divided into three parts, dried and assayed. The reject was retained for testing purposes. From the depth of the auger holes a contour map of the dump was plotted, Fig. I, which gives percentages of tonnage and copper content. The tonnage within the limit of the drill holes was estimated at about five million tons with an average content of 0.42 per cent Cu, 31 per cent of which (0.13 per cent) was acid-soluble. A screen analysis of the composite dump sample is shown in Table I. Flotation tests by several companies and individuals were then made, the results of which ranged from 62 to 74 per cent recovery. On the basis of these, a 200-ton pilot plant employing straight flotation was built and operated for a few months. Operation of this plant was unsuccessful, as no provision had been made to handle the copper-bearing solutions resulting from the water-soluble copper, a point that was overlooked in the laboratory test work. Attempts to decant the copper-bearing solution for precipitation in the usual manner ahead of flotation were not satisfactory because of low water recovery (owing to poor settling characteristics of the pulp) and contamination of the copper precipitate with unsettled slime. Low copper prices in 1931 necessitated the termination of testing. With the stimulus of higher copper prices in 1937, a review was made of metallurgical

Jan 1, 1943

By L. R. Blair

Many hydrated silicates have been synthesized and sold for commercial use. However, this paper discusses only hydrated calcium silicates and, to a lesser extent, hydrated magnesium silicates. Synthetic calcium silicates were first formed by man when he found that mixtures of silica or silicates and lime in water set up to form cements. The material which was responsible for the cementing properties was calcium silicate hydrate, although this fact was not recognized until early in this century. In the early 19001s, synthetic calcium silicates, reinforced with fibers and formed simply by reacting calcium hydroxide and silica in water with fiber at atmospheric or under low pressure autoclave conditions, found increased use in thermal insulations and in building products. These insulations were found to have a low thermal conductivity and would withstand temperatures up to 650°C. This, combined with their very low densities (from 8 to 50 Ib per cu ft) and fairly high strength, also made them suitable for use as building products. Following the disastrous Morro Castle fire of the 1930Js, calcium silicate board products were used as partitioning material in all shipboard construction in the U.S. As autoclaving techniques were improved and developed, it was: learned that under hydrothermal conditions new and useful calcium silicates which could be used under more extreme temperatures (up to 980&apos; C) could be prepared. These had high surface areas and other unique properties which suited them for use as fillers, pesticide carriers, low temperature insulating materials, and adsorbents for the removal of fatty acids from various solutions. Hydrated magnesium silicates have not been studied as extensively as the calcium compounds. Their first important use was in the filtration of dry cleaning solutions for the removal of fatty acids. With the introduction of detergents, it was found that these products lost their advantage because of their high affinity for the detergent chemicals. However, in recent years these chemicals are finding increasing use as decolorizing agents for fats and anti-caking agents for resins. Some materials with very high surface are finding new use as adsorbents. CALCIUM SILICATE HYDRATE COMPOUNDS AND THElR CONDITIONS OF FORMATION Within the past ten years much has been done in the field of calcium silicate hydrate chemistry. As a result of this work it has been found that at least 25 different forms of calcium silicate hydrate can either be formed synthetically or found as naturally occurring materials. The stability and composition relationships among these 25 compounds present a very complicated picture, and many of these very closely resemble other forms and are difficult to dis-

Jan 1, 1962

By C. S. Barrett, D. F. Clifton

THE transformation that occurs in lithium and its solid solutions containing magnesium1,2 is similar in many respects to other diffusionless transformations of the martensitic type. This general similarity makes it desirable to investigate the transformation curves in detail. The current interest in the phenomenon of stabilization in martensitic transformations has created a need for a careful appraisal of possible stabilization effects in both cooling and heating transformations in lithium alloys. The effect of prior heat treatment on the temperature at which transformation begins and the effect of various temperature cycles in partially transformed alloys also merit attention. Limited data on some of these features were presented previously,&apos; but the present studies have been made with improved apparatus, in which erratic fluctuations were smaller than in the earlier work, and include many independent determinations of certain critical observations. Material and Methods Geiger counter X-ray spectrometers were used: a Norelco instrument, original model, and a General Electric XRD-3. The low-temperature specimen holder has been described elsewhere." Specimens 10 mm in diam and 1.5 mm thick were held in firm contact with a copper block which was attached to the lower end of a stainless steel tube that extended up to a reservoir of liquid nitrogen. A heating coil on the tube permitted a controlled temperature gradient along the tube, so that desired temperatures and rates of heating and cooling could be obtained by controlling the heating current. The specimen was surrounded by an atmosphere of evaporated nitrogen in an insulated chamber having double cellophane windows. The temperature of the specimen was read by a thermocouple imbedded in it close to the irradiated area; the specimen could be held at constant temperature within 1°C for long periods. The body-centered cubic 200 reflection near 8 = 26" was used as the index of the amount of b.c.c. material present; occasional checks were made using the most suitable line of the low-temperature phase, the close-packed hexagonal 110 line near 8 = 29". Copper radiation was used throughout. A continuous record was made of the reflected intensities on a strip chart recorder, both when the peak intensity of a line was being followed and when the lines were being scanned at constant temperature. On the continuous recordings of peak intensity, periodic checks were made on the background intensity between the lines, and on the setting of the spectrometer for maximum intensity. The lithium-base solid solution containing 12.4 atomic pct Mg (33.3 wt pct) that had been used previously&apos; was chosen, as it had a transformation range at relatively high temperatures, so as to permit wide temperature cycling within the range. Just prior to use a pellet was cut from the ingot,

Jan 1, 1951