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By R. W. Guard, M. E. Fine

By treating the dislocation like a surface and ap-plying the usual thermodynamic treatment to the adsorption process a Gibbs adsorption equation for dislocations was derived. For extended dislocations in binary solutions the adsorbed concentration on the fault, X2a, may be computed from (jo/da2b) where a2b is the activity of the solute in the bulk material and s is the stacking-fault energy. Using the data of Howie and Swann for s the adsorption concentration goes through a maximum at 2 at. pct Al in Ag-Al, 10 at. pct Zn in Cu-Zn, and 8 at. pct A1 in Cu-Al. The pinning stress calculated from this concentration difference goes Ihrough a maximum at the same concentration us the peak in X2 a. The computed pinning stress thus does not vary with composition in the manner predicted by Suzuki, as was also pointed out by Hendrickson. The results are compared with the stress increment which can be attributed to Suzuki locking in Cu-Zn and Cu-Al stress-strain curves. They both agree in magnitude and in the location of the maximum. The predicted and observed maximum values for the Cu-Zn system (where activity data are available) are 700 g per sq mm (predicted) and 1000 g per sq mm (measured, laking into account the orientation factor of 2.2 to convert poly-crystalline to single-crystal data). CERTAIN simple internal surfaces may be regarded as dislocation grids. This fact suggested that it might be profitable to consider certain phenomena related to segregation of solute atoms at dislocations from the point of view of the thermodynamics of surfaces and surface adsorption. A general treatment of this type is given and then the results are applied to Suzuki segregation and pinning. Confirmation of the results is obtained from comparison of stress-strain behavior for copper and copper-base alloys. Two kinds of dislocations need be treated: perfect and extended dislocations. In either case the line tension of a dislocation, ?. the work which must be done to increase the length of dislocation by a unit length, is analogous to the surface tension. For an undissociated dislocation ? is the self-energy of a unit length of dislocation; for an extended dislocation where is the self-energy per unit length of a pair of partials far enough apart so that there is no interaction energy, is the interaction energy per unit length, is the stacking fault energy per unit area, and w is the equilibrium separation of the paired partials. In the absence of an applied stress the force pushing the dislocation partials apart in a close-packed structure is Gb2/12p where G is the shear modulus, b is the Burgers' vector of the complete dislocation, and is the separation of the partials. At the equilibrium separation, w this force equals s. Thus

Jan 1, 1965

By T. D. Murphy

The element silicon, with its usual partner, oxygen, plays the same role on this planet relative to inorganic materials as carbon and hydrogen play with respect to living organisms. The crystallographic structure of silicon dioxide (SiO,) consists of one atom of silicon well-nigh inseparably bonded to four contiguous atoms of oxygen, a gas of but slightly more than half its atomic weight, forming a three-dimensional network of SiO, tetrahedra (Dietz, 1968). This wispy arrangement is the fabric of the mineral quartz which is one of the harder, more abrasive, and chemically stable raw materials to be found in Mother Nature's cupboard. Most of us are vaguely familiar with the observation that nearly 60% of the lithosphere to an approximate depth of 10 miles is composed of these two elements, which proportion actually rises to about 75% if the atmosphere, hydrosphere, and biosphere are included (Parker, 1967). Elemental silicon is a brittle steel-gray metalloid with a density of 2.42 and does not occur in nature. In its limited commercial form, which is still brittle and metallic in appearance, its density drops to 2.33. It combines with oxygen to form the gaseous oxide SiO, or the solid dioxide SiO, (analogous to its congener carbon in CO and CO,); a tetrachloride SiCl, (analogous to CC1,); or, combining with oxygen and one or more metal ions, forms the largest rock-making family of all, the silicates. Further, next to the feldspars, quartz is the most abundant known mineral and, in some form or another, accounts for roughly 12% of surficial terrestrial rock. It is this so-called "free silica" to which your attention is chiefly directed in this chapter. In any such consideration of silica, its several crystalline phases with their attendant differing physical properties appear worthy of delineation. Alpha quartz is the only one of this interesting polymorphic family that is thermodynamically stable at normal pressures and temperatures up to about 573°C. The low phases of tridymite and cristobalite can exist in the so-called metastable state below 117°- 200°C but seldom occur in nature in these two different crystal forms (Sosman, 1965). Opaline silica, now considered by most researchers to be a variety of cristobalite, occurs in abundance and is the only exception. The three remaining polymorphs, keatite, coesite, and stishovite, also are metastable under ambient conditions. Keatite, however, is not known to occur naturally and has only been synthesized in the laboratory. The other two have been identified in submicron sizes and in microscopic amounts, occurring naturally as a result of high order shock-wave pressures generating quite elevated temperatures-such as might accompany the impact of a large meteorite on a hard sandstone terrain (Chao, et al., 1962). An intriguing characteristic of these silica minerals, and one which has very practical applications, is their extremely variable densities. The classic 2.65 specific gravity of alpha quartz drops to 2.20 in tridymite, cristobalite, and lechatelierite (natural silica glass), as well as in many man-made glasses of commerce which are merely noncrystalline or amorphous solids in the form of super-cooled liquids which can no longer change their shapes (Pauling, 1950). It rises again to 2.50 and 2.93 for keatite and coesite, respectively, and finally becomes a reported 4.35 for stishovite-nearly a 50% range in density for the known physical combinations that silica naturally assumes (Frondel, 1962; Konnert, et al., 1973; Pecora, 1960).

Jan 1, 1975

By James W. Shaffer

Aluminum is the most abundant metallic element of the earth's crust and is a constituent of nearly every type of rock (Clark, 1924, p. 13). The sources of aluminum and aluminous material most commonly used by modern industry are the bauxitic raw materials consisting of bauxite, bauxitic clay, and aluminous laterites. These are mixtures of hydrated aluminum oxide minerals and mineral impurities. End Uses Bauxite is used as an aluminum ore and in the manufacture of refractory products, aluminous chemicals, and abrasives. Other raw materials are used for aluminum ores, but their use is minor compared to bauxite. Refractory products made from bauxite are synthetic mullite, high-alumina fire bricks, castables, monoliths, cements, and ramming mixes used by the iron, steel, and cement industries. Chemicals made from bauxite are aluminum sulfate and sodium aluminate for water treatment and aluminum chloride used in refining crude petroleum. Among the abrasive products made from bauxite are coated abrasives, sharpening stones, and grinding wheels. Special grades of bauxite are used in the decolorization and clarification of raw sugar and lubricating oils. Bauxite has been used for road surfacing but mainly because other material was not more readily available. Perhaps the oldest use of bauxite and aluminous laterite is for a building stone. Ancient temples and more recent structures in India have been made from these and some varieties are suitable for decorative stone. Geology Mineralogy and Properties – Bauxite is a mineral raw material composed principally of one or more hydrated aluminum oxide minerals and impurities of silica, iron oxide, titania and elements in minor or trace amounts. The hydrated aluminum oxide minerals are gibbsite, boehmite and diaspore. Corundum is not included as a bauxite mineral although it does occur in some bauxite deposits. Boehmite and diaspore are both alumina mono-hydrates and have essentially the same composition, but diaspore has a greater hardness and a higher specific gravity because of a more tightly bonded and compacted atomic structure. Gibbsite is an alumina trihydrate mineral. Properties of bauxite minerals are shown in [Table 1].

Jan 1, 1975

By C. D. Hall, F. E. Dollarhide

Fluid Ioss agent.s for crude oil and for water have been studied in dynamic tests. A treatment using a spearhead with a fluid loss agent followed by plain fluid appears feas ible in crude oil, but not in water. An equation for spearhead depletion shows that spurt loss relative to fracture width must be low, if the portion of spearhead fluid in the treatment is to be small. The presence of colloidal matter in crude oils aids the fluid Ioss agent. Unlike in kerosene, where flow limited the agent deposition, in crude oils the filter cake continually formed and leak-off declined. The volume-time relation varied somewhat for different crudes, but was best described by a square root of time function. Spurt loss was inversely proportional to agent concentration. After the fluid loss agent initiated the filter cake, the crude oil colloids built on it effectively. A 2-minute or a 5-minute spearhead with double the normal agent concentration gave the same fluid Ioss curve as the same concentration did for a 30-minute test. The agents tested in water gave fluid Ioss plots on which, for the first few minutes, volume was proportional to the square root of time, but later became proportional to time. For fracture area calculation the customary square root of time function is a satisfactory approximation. Leak-off rates and spurt losses were higher in water systems than in oils. The spurt Ioss tended to be inversely proportional to concentration. In spearhead tests, the filter cakes were not eroded by water flow. However, the rather high spurt loss values make spearhead treatments impractical for water-based fluids. Introduction The effects of dynamic testing conditions on the performance of fluid loss agents in kerosene have been studied previously.' We have extended the work to include crude-oil- and water-based fracturing fluids. An understanding has been gained of the mechanisms of formation and functioning of the filter cakes of fluid loss agents. The practical aspects of evaluating performance of agents in relation to fracture area calculations also are considered. The feasibility of using the fluid loss agent in a spearhead stage of the treatment is examined further for both types of fluids. Experimental Procedure The dynamic fluid loss tests were performed in an apparatus similar to the high-pressure apparatus described in a previous publication.' A fracturing fluid was circulated over a rock surface located in a closed pressurized loop. The fluid flowed axially over the cylindrical surface of a core 2 in. in diameter X 3.5 in. long, mounted (with the flat ends sealed off) in a pipe, with 0.117 in. annular clearance. The filtrate was collected in a central hole in the core and led through valves to graduated cylinders. Provision was made for changing quickly the circulating fluid during the test (spearhead runs) without interrupting the filtration pressure. The only modifications were to add heating tapes and water jackets for the tests with crude oils, all conducted at ISOF, and to change all parts exposed to the test fluid to stainless steel for the tests with water-based fluids. The latter tests were made at room temperature, 80F. Three crude oils were tested. A mixed crude, obtained from a local refinery, contained a considerable amount of light ends. For safety reasons, it was stripped to 250F vapor temperature before use in the fluid loss tests. The other two oils were used as obtained from lease tanks. One was a greenish-brown, 37" API paraffinic crude, and the other was a black, 32" API asphaltic crude. The fluid loss agent for oil, here designated for brevity as Agent A, was Adomite@ Mark II*, a granular solid commercial agent, the same as previously tested in kerosene.' Three different compositions of fluid loss agents were tested in Tulsa tap water. Agent B was adomit& Aqua*, a solid commercial fluid loss agent, comprising clays and hydrophilic gums principally derived from starch. Agent C was a mixture of three parts of Agent B with two parts of silica flour. Agent D was Dowel1 J137, a mixture of guar gum and silica flour. The test cores were cut from contiguous blocks of Berea or Bandera sandstones. For the oil tests, the cores were oven dried, evacuated, saturated with kerosene, and the kerosene permeability was measured. The cores used with the water-based fluids were pretreated by saturating with 3 percent calcium &loride solution to minimize pemeability damage by the fresh water due to clay migration. The

Jan 1, 1969

By E. P. Klier, Jane Jellison

The course of the transformations on cooling in a series of Cu-A1 alloys has been followed by means of thermal analysis, X-ray diffraction, and optical metallogrAphy. Specimen size was found to have a pronounced effect on the time of completion of the pearlite transformation due to modification in the unmber of nuclei. The ordeving transformation zvas observed for all cooling rates for all alloys studied, and is considered insuppvessible. At intermediate cooling' rates, a transitional struchire for 011 alloy compositions and based ox the bainite reaction was observed. The alloys of aluminum and copper possess a eu-tectoidal region at from about 9.4 to 16 pct Al. Above the critical temperature, the disordered bcc phase, 0, is stable. At subcritical temperatures, the 0 phase decomposes under equilibrium conditions into the stable phases, a and y,. At the eutectoid composition, these phases develop a lamellar pearlite structure, in appearance much like that found in steels. During rapid quenching from supercritical temperatures, the diffusion processes required for the formation of the equilibrium phases are suppressed, and the 0 transforms to an acicular martensitic phase, designated B or y' depending on the aluminum content, or to a mixture of the two. Early investigators of this system concentrated on determining the equilibrium phase diagram, ''' the structure of the equilibrium phases,3 and later the isothermal decomposition of the 0 phase at subcritical temperatures, or the decomposition of the martensite on tempering. Other work which treated the nonequilibrium transformations concentrated largely on the martensite transformations and the structure of the b and y' phases.15"17 Since the pearlite and martensite transformations in this system resemble those in steels, the one being formed by nucleation and growth of adjacent lamellae of the equilibrium phases, and the other by a diffusionless, shear-type transformation, the present study has been undertaken to investigate the structures formed on continuous cooling, with the objective of constructing cooling transformation diagrams analogous to those derived for alloy steel systems. In particular it was desired to determine whether parallels between the A1-Cu and iron-iron carbide systems on continuous cooling extended to encompass the intermediate phase, namely the bainite structures, which form by a combined martensitic-diffusion mechanism,'' but which are supersaturated with respect to the equilibrium phase upon which their crystal structure is based. To this end the transformations in representative alloys of the Cu-A1 B eutectoid system have been followed, using the methods of thermal analysis, X-ray diffraction, and optical microscopy. EXPERIMENTAL PROCEDURE Materials. The materials tested were those used by Klier and Grmko 5 in their study of the isothermal decomposition of these alloys. The alloys were melted in graphite crucibles and chill-cast into 5 by 2 by 1/4 in. ingots. The ingots were then hot-rolled to sheets 1/8, 1/16, and 1/32 in. thick. The compositions are given in Table I. Specimen Preparation. Specimens for thermal analysis were in the form of small squares approximately 1/4 in. on a side. For the 11.9 and 13.5 Al-Cu alloys, the sheet thickness was 1/16 in. and for the 10.5 A1-Cu alloy the 1/32-in. sheet was used. One lead of a chromel-alumel thermocouple was spot-welded to either face of the square with the specimen itself thus forming the hot junction of the thermocouple. Specimens for X-ray analysis were prepared as filings from martensitic sheet stock and were sealed in glass ampoules under 1/2 atm of argon. Metallographic examination of the powder specimens was carried out on a portion of the heat-treated filings mounted in lucite. All specimens were examined metallographic ally after etching

Jan 1, 1965

By G. O. Prickett, P. Somasundaran

An experimental progmm based on statistical principles is used for optimizing a flotation operation for the separation of minerals. In this case, flotation of sylvite from sylvinite ore with amine and starch as the flotation reagents was studied to find the optimum reagent levels at various slime levels. The experiments were first done on a two-level three-factor design. Analysis of the results showed that the interactions between various factors were significant. Hence, a first-order linear model of the flotation response would not be accurate. The two-level three-factor design was expanded into a composite design in order to test the fit of a higher-order model. Data were treated to obtain an expression for flotation response as a function of the different variables, to predict the optimum reaaent levels at various slime levels, and also to determine the path of steepest ascent. Tests around the predicted optimum and along the path of the steepest ascent were done until a near-optimum region was obtained. Exploration of the nature of the response surface in that region established the actual location of the maximum response. The optimum amine level was found to be 0.20 lb of amine per ten of ore at all slime levels, while the optimum starch level varied as a function of the slime present. Computer access at the laboratory by means of a teletype terminal on a commercial time-sharing system enabled efficient and accurate treatment of experimental data. The efficiency of experimental investigations can be improved significantly by the use of experimental design and data analysis based on statistical principles. The common approach used in experimental research is to study a property of a system as a function of "one-variable-at-a-time". Several authors'-4 have pointed out the inadequacy and deceptiveness of this method. Results obtained for the effects of a variable on the measured response of the system using

Jan 1, 1970

By Charles Fulton

EXPERIMENTAL work on the process was begun on a laboratory scale at Cleveland, Ohio, in 1914, and transferred to East St. Louis, Ill. in 1916, where a commercial sized furnace was in technical operation until January, 1918. The essential steps of the process are as follows: Oxidized zinc ore or roasted zinc concentrate is mixed with crushed coke and coal-tar pitch and formed into briquets 9.25 in. (23.5 cm.) in diameter and 21 in. (53 cm.) long in a manner similar to that used in the manufacture of graphite or carbon electrodes, except that much less care and time are required. The composition varies with the nature of the ore; in one case, the composition was 100 parts ore, 70 parts coke, and 18 to 20 parts pitch. These briquets maintain their form and volume during and after the distillation of the zinc. This object is gained by using coke as the matrix and coal-tar pitch as the binder; this pitch becomes coke on heating and unites the ore particle and the original coke particle into a continuous mass. The briquet is an electrical conductor but only to such, a degree that it can be used as a resistor. The size of the ore, as in the present practice of zinc metallurgy, ranges from fine material, such as flotation concentrate, to coarse table and fine jig concentrate. The process is not restricted to any particular kind of ore, but is applicable to pure high-grade ores, ores high in iron, and complex zinc lead ores, since the residue from the distillation is held immovably in place within the briquet. In the case of complex zinc-lead ores, the distillation is conducted with a carefully regulated temperature so that a high percentage of lead is retained in the distilled briquet, which may then be smelted for its lead content. In present zinc smelting practice, the reduction fuel is from 40 to 50 per cent. of the weight of the ore. In the briquet, it is from 60 to 85 per cent. of the ore; but unless the ore is exceptionally high in residue, the distilled briquet

Jan 9, 1919

By B. M. Larsen, K. Heindlhofer

THIS paper describes a relatively simple electrical apparatus that, through the close analogy between the flow of heat and of electricity, enables one to solve quickly and with satisfactory accuracy many complex problems in heat flow. This device, developed in 1935, has proved especially useful in the solution of certain practical problems relating to the design and efficiency of regenerators for an open-hearth furnace or coke oven, yielding within a few hours information that would take weeks or even months to acquire by mathematical1.2 or experimental3 methods of comparable accuracy. Its description now is prompted by growing interest in such analogues, as shown by several recent papers.4.5 The analogy between flow of heat and of electricity appears to have been recognized first by Maxwell who, in his famous Treatise on Electricity and Magnetism (1881) says: The analogy between the theory of the conduction of electricity and that of the conduction of heat is at first sight almost complete. If we can take two systems geometrically similar, and such that the conductivity. for heat at any part of the first is proportional to the conductivity for electricity at-the corresponding part of the second, and if we also make the temperature of any part of the first proportional to the electric potential at the corresponding point of the second, then the flow of heat across any area of the first will be proportional to the flow of electricity across the corresponding area of the second. .. Thus, in the illustration we have given, in which flow of electricity corresponds to flow of heat, the electric potential to temperature, electricity tends to flow from places of high to places of low potential, exactly as heat tends to flow from places of high to places of low. temperature He noted, however, that this analogy is restricted: ... there is, however, one remarkable difference between the phenomena of electricity and those of heat. Suspend a conducting body within a closed conducting vessel by a silk thread, and charge the vessel with electricity. The potential of the vessel and of all within it will be instantly raised, but however long and however powerfully the vessel be electrified, and whether the body within be allowed to come in contact with the vessel, or not, no signs of electrification will appear within the vessel, nor will the body within show any electrical effect when taken out. But if the vessel is raised to a high temperature, the body within will rise to the same temperature, but only after a considerable time, and if it is then taken out it will be found hot, and will remain so till it has continued to emit heat for some time. The difference between the phenomena consists in the fact that bodies are capable of absorbing and emitting heat, whereas they have no corresponding property with respect to electricity. According to this statement the application of the analogy would be limited to problems of steady flow that do not involve heat-capacity effects. In spite of this

Jan 1, 1945

By Paul A. Bailly

Around 4500 B.C., the Pharaoh of Egypt ordered a military campaign to the Sinai Peninsula and the shores of the Red Sea, to search for copper deposits which Egypt needed for jewelry, vases and weapons.5 To my knowledge, this is the first recorded expedition aimed at the discovery of minerals. The diligent Egyptian soldier-prospectors made discoveries through visual detection and manual effort, the approach which has given us the bulk of our mines to date. In the Rio Tinto District of Spain where Roman miners followed the Phoenician traders, we find the first evidence of discovery of hidden ore bodies in the absence of mineralized outcrops. This is how Joralemon 13 describes these Roman discoveries to the southwest of the Rio Tinto hills, under the flat plain of Seville:

Jan 6, 1979

By Frederick Laist

THE ore from the Butte mines of the Anaconda company is quite siliceous; that is, it contains considerably less iron than is needed for the fluxing of the silica. The direct smelting of this ore, therefore, requires the addition of considerable fluxing material. The only flux available in sufficient quantity at Anaconda is limestone containing no metallic minerals. This necessarily makes the direct smelting of the ore so expensive that it is more profitable to subject the ore to a preliminary treatment by concentration. However, as the losses in the concentrator were very high, compared with the losses in the blast furnaces, it was found, by calculation, more profitable to send ores containing more than a given percentage of copper to the blast furnaces, in spite of the higher costs of treatment. The dividing point was dependent on various factors, the chief of which was the prevailing market price of -copper. It was customary, therefore, to segregate the ore as mined into two classes. Ore in the first class generally contained 5 per cent. or over of copper;: this was sent directly to the blast-furnace department. Second-class ore contained less than 5 per cent. of copper, and averaged around 3 per cent.; it went to the concentrating department. With the introduction of the flotation process, it was found possible to maintain an average recovery, as concentrates, of 96 per cent. At the same time, the cost of reverberatory smelting was very materially decreased by the use of pulverized coal. These two changes in practice made the blast furnaces unable to compete with the reverberatory furnaces on a cost basis. The distinction between first-.and second-class ore was therefore abandoned, and the ore was treated by concentration. Obviously, on ores as high in iron as the Butte ores, the concentrator, produces a product that is self-fluxing; in fact, it is possible to produce a

Jan 1, 1920

By H. S. Greismer

Alabama washes a larger percentage of its total coal output than any state in the Union. For producing coking coal, three-compartment jigs are favored; mines providing, steam and commercial coal use single-compartment jigs exclusively. Chemists are as necessary to washing plants as recording gages are to power plants. Experiments in Alabama indicate that the sludge released by coal-washing plants can be deposited in streams and on agricultural lands without disastrous results. CAMPBELL, 1 in 1896 said: "The Birmingham district in Alabama has certain great advantages for there are few places in the world where fuel and ore are so near together, although, unfortunately, both are of inferior quality; the ore being low in iron and high in phosphorus and the coal giving a weak and impure coke." This statement could not have been, questioned in 1894, but by 1896 several Robinson-Ramsay washers had been put into operation and weak and impure coke was a thing of the past. The Warrior coal field of Alabama contains six seams that yield coking coal of excellent quality. In descending- order, they are Brookwood, Milldale, Pratt, America, Mary Lee, and Black Creek. In each of these, however, bands of rock and bone coal of varying thickness are stratified with the coal; and while some of these impurities can be separated from the coal by the miner, much of it must be loaded out with the coal: Consequently, unless the coal is washed before being coked, it will yield a coke of varying ash and sulfur content quite unsatisfactory, for blast-furnace use. At present, the Gulf States Steel Co. is producing run-of-mine coal at its Virginia mine, from the America seam, that is uniformly low enough in ash to permit of coking without washing, but this is the only exception to the above statement. Alabama was the first state to experiment seriously with coal washers, was the first to install washers on a large scale and, up to the present, has maintained the lead. The Alabama State Mine Inspector reports that during 1923 20,919,303 tons of bituminous coal were mined in Alabama; 12,858,499 tons of which were delivered to coal washers for treatment.

Jan 9, 1924

By Glenn Allen

SAN FRANCISCO Mines of Mexico, Ltd. owns and operates an extensive group of claims in the San Francisco del Oro-Santa Barbara district, about 15 miles southwest of Parral, Chihuahua. The property comprises the mines, aerial tramways, flotation mill, power plant, shops, offices, assay and testing laboratories, modern hospital, water and sanitary system, quarters for miners, mechanics and operators, a well housed colony for Mexican staff employees and residences for foreigners. Each colony has a club house and mess and tennis courts. The employees have constructed a nine-hole golf course. In other words, the property is self-contained and completely integrated for production of lead and zinc concentrates from complex sulfide ores.

Jan 1, 1930

By Samuel Daniels

THE Al-Cu-Ni-Mg alloy is much benefited by heat treatment and, in such con¬dition, is preferable to the Al-Cu-Fe-Mg alloy either as cast or as heat-treated, when both are reheated to temperatures of from 400° to 600° F. and compared, cold, with respect to strength and to hardness. The main differences between the alloys do not arise until the reheating temperature exceeds 400° F., above which they gradually soften. This softening is characterized metallographically by the appearance of intragranular precipitate. The Al-Cu-Ni-Mg alloy is weakest and least hard after being reheated at 600° F., the AI-Cu-Fe-Mg alloy at about 700° F. The former starts to reharden at 700° F., the latter at 800° F. There is a tendency for both alloys to lose strength and hardness with prolongation of time at the reheating temperatures of 500° and of 700° F. The Al-Cu-Ni-Mg alloy is considerably stronger and harder than the Al-Cu-Fe-Mg alloy when both are heat-treated and reheated for long periods of time at 500° and 700° F. Although the latter can be made harder initially than the AI-Cu-Ni-Mg alloy by suitable quenching and aging, heat treatment, in general, favors the retention of this initial (strength and) hardness after reheating to a much greater degree in the Al-Cu-Ni-Mg alloy. The percentage of elongation of the two materials in any condition is very small. CERTAIN aluminum alloys have been used for pistons and other parts operating at temperatures up to 650° F. because of their lightness, high thermal conductivity and specific heat, fair strength and hardness at elevated temperatures, excellent machineability, and moderate resistance o corrosion. In the piston, the inertia forces and the bearing loading and with this the vibration are decreased. The piston head functions at a lower temperature (about 200° F. below one of cast iron), so that, because of the lessened tendency toward carbonization and detonation, higher compression ratios may be used. On the other hand, the aluminum alloys do not have the wearing and bearing qualities of cast iron; also they have a large coefficient of expansion, allowance for which must be made in the design.

Jan 2, 1926

By Tibor Stefansky, John E. Dorn

MOTT and Nabarro1-5 were first to illustrate the importance of the flexibility of dislocations in accounting for the strengthening that metals undergo due to the presence of internal-strain centers. Such strain-centers might arise from a number of causes such as radiation damage, the presence of semicoherent and coherent precipitates and clusters, as well as individually dispersed interstitial and misfit substitutional solute atoms. Each strain-center induces positive and negative shear stress fields on the slip planes of the surrounding alloy matrix. In order to effect plastic deformation, therefore, the alloy must be subjected to sufficiently high applied shear stresses to push dislocations past all such internal stress fields. If dislocations were inflexible and moved as rigid lines, they would be equally pushed and pulled by internal stress fields. At this extreme the strengthening would be vanishingly small. Dislocations, however, are not rigid; they are flexible and extensible. They wiggle between positive and negative strain-centers, thus increasing their line energy at the expense of their interaction energy with strain-centers. cottrel16 and Friedel7,8 have independently presented lucid reviews of the significance of the Mott-Nabarro dislocation-flexibility concept to the strain-center strengthening of alloys. Their analyses however were only semi-quantitative. There is evidence in the recent literature of renewed interest in a more rigorous analysis of flexibility. Thus, Gleiter9 and Gerald" have shown that the calculated strain-energy interaction between a dislocation and the stress fields of coherent precipitates can be seriously in error if the flexibility of the dislocation is not taken into account. This report will be concerned with a more detailed analysis of the problem based on the following approximations: 1) Although many types of strain-centers exist, the following analysis will be limited to the case of solute-atom strain-centers in fcc substitutional alloys. 2) To facilitate the analysis by avoiding statistical considerations, the strain-Centers are assumed to be in regular arrays on the slip plane. Although the quantitative results are somewhat dependent on the type of array that is assumed, the qualitative trends are similar for various arrays that were studied. 3) An adjustment of the results from those for square arrays to those for the more realistic case of a random distribution of strain-centers is accomplished by adopting the interesting statistical theory first introduced by Kochs,11,12 elaborated on by Dorn, Guyot, and stefansky,13 and analyzed by Foreman and Makin14 in their computerized experiments. 4) For simplicity the dislocation lines are taken to wiggle about their edge orientation and no correction is applied to their line energy for deviations from edge configurations or for the elastic interaction between segments of the now curved dislocation. It will be shown that for extremely low concentrations of atomic strain-centers the strengthening increases with the square root of their concentration. For slightly higher concentrations the strengthening rate becomes less rapid. At a critical concentration a maximum strength is obtained and a decrease in the strengthening takes place as the concentration of solute atoms is further increased. These trends are a direct consequence of dislocation flexibility. They arise from changes in the amplitude of the waviness of the dislocation line at the yield stress with solute atom concentration. Despite the simplifying assumptions that were made, the results agree qualitatively with appropriate experimental data. I) STRESS FIELDS ON SLIP PLANES Internal stresses are introduced in a lattice whenever a host atom of radius ro is replaced by another that has a different atomic radius. According to the classical theory of linear elasticity,15 the stress field about a solute atom at the origin of a spherical coordinate system is given by arr=-4G€(?_0)3 ffflfl ="W =2G€{t) f°rr^ro(l+e) UJ where G is the shear modulus of elasticity and Y, = ro(l + E) is the radius in situ, of the substituted atom. As shown by ~shelb~,'~ this approximation assumes that the bulk modulus of elasticity of the substituted atom is identical with that of the host species. ~abarro'~ suggested that the strain E can be deduced

Jan 1, 1970

By L. S. Darken

A quadratic formalism is developed lor the representation of the excess free energy, and of the activity coefficients of each component of a ternary system in the vicinity of a single component selected as solvent. This formalism, in contrast to the e formalism, is thermodynamically consistent at .finite concentrations. Numerous specific systems are used as illustrations, with cross checks where possible; these systems are Fe-C-X systems in the vicinity of 1600°C and include practically all those for which reliable data are available. It is shown that this formalism is usually quite adequate to rebresent available data up to a solute concentration of 20 to 30 at. pet. It is hoped that the formalism here presented may prove useful for the treatment and tabulation of data on ternary and multi-component solutions. SINCE, as discussed in a prior paper,' we do not as yet have an adequate basic understanding of the nature of binary metallic solutions, we cannot hope to be in better position for ternary and multicomponent systems. However, the accumulation of thermodynamic data on ternary and multicomponent metallic solutions has led to an urgent need for a rational formalism for the presentation and use of such data. Notable attempts to represent the isothermal isobaric thermodynamics of ternary solutions were made by Benedict et 01.' and by Wohl.3 These attempts were directed toward developing an analytic expression adequate to encompass the entire ternary triangle, primarily for organic systems; they generally involve the power-series approach, which has been shown' to be inappropriate, in general, even for binary metallic systems. On the other hand, interest in the thermodynamics of ternary and multicomponent metallic solutions has tended to focus either on general thermodynamic relations4-10 over wide compositional ranges, or on cases where one or more components have been at rather low concentration. This latter approach has been followed by Wagner,= by chipman,11 and by Alcock and Richardson,12 and more recently in many publications by the same and other authors. It has already been shown' that the thermodynamic behavior of binary metallic systems is, in general, relatively simple only in the terminal regions. Hence, it would appear that any approach, at this time, to a simple formalism for ternary and multicomponent systems must, a fortiori, be limited to the vicinity of the major component or solvent. The present treatment is aimed to be useful for a given solvent with moderate solute concentrations ranging up to 20 or 25 at. pet and in exceptional cases to considerably higher concentrations. In order to achieve even this modest objective, it is necessary that any appropriate formalism have built into it 1) a thermodynamic consistency (at least within the desired degree of approximation), and 2) an approach at infinite dilution to Raoult's law for the solvent and to Henry's law for each solute. Let us first formulate the condition of thermodynamic consistency for a ternary system. Under isothermal isobaric conditions, we may write for the molal value G of any extensive function dG - C1 dN1 + G2 dN2 + G3 dN3 [l] where the G's are the corresponding partial molal quantities and the N's are the atom fractions. Taking component 1 as the solvent, this relation may be rewritten in terms of the independent variables N2 and N3

Jan 1, 1968

By P. A. Beck, S. Kohara, M. N. Parthasarathi

IT has been shown1,3 that many observed phenomena related to annealing textures in f.c.c. metals can be adequately accounted for, at least in a qualitative way, by considering the orientation dependence of the boundary mobility, without any hypotheses concerning preferred orientation of nuclei. It was noted1 that this approach is particularly successful in the common cases of primary recrystallization in highly cold-worked polycrys-talline metals, where nuclei occur in great abundance, and that in the other extreme case, where the number of nuclei is very limited, or even only a single crystal is grown, the orientation dependence of boundary mobility has only a small effect, or none at all, on the orientations resulting from annealing. Recently Dunn described examples3-6 where observed secondary recrystallization textures apparently cannot be accounted for on the basis of oriented growth alone, but also require oriented nuclei, or at least the absence of nuclei in certain orientation ranges. In general, the great difficulty in correlating the preferred orientation of recrystallized grains with that of nuclei is inherent in the fact that nuclei are by nature very small, and that they are usually identifiable as "nuclei" only after growth, i.e., after they have already been subject to growth selectivity. An investigation was carried out by Liebmann and Lücke,' and also a very similar one by Graham and Cahn,' to obtain quantitative information on the orientation depend- ence of boundary migration rates in the recrystallization of slightly deformed aluminum single-crystal rods or plates, in which artificially nucleated recrystallized grains of predetermined orientation were grown. Liebmann and Lücke foupd maximum boundary mobility for boundaries across which the misorientation corresponded to a rotation of 40 deg around a common [Ill] axis, in accordance with earlier conclusions.9,1 Also, they confirmed that such an orientation relationship predominates among crystals growing into slightly extended single crystals from presumably random artificial nuclei. On the other hand, Graham and Cahn found no preferred orientation among crystals grown in a similar manner. It is not as yet known how these observations may be reconciled with each other. The view has been expressed in various papers5'10,21 that selective growth based on the orientation dependence of boundary mobility is not in itself sufficient to account for the formation of sharp re-crystallization textures, such as those often observed in highly deformed polycrystalline metals after annealing. The present work was undertaken to ascertain whether or not it is possible to obtain a sharp re-crystallization texture in a case where random nuclei are assuredly present in large numbers. It was previously found1' that high-purity aluminum crystals rolled 80 pct on the (110) plane in the [1T2] direction, when suitable precautions are taken, may be annealed for periods of about 1000 sec at 350°C without recrystallization. It was also found that the reluctance to recrystallize in this case is due to the scarcity of material in sufficiently deviating orientations to serve as nuclei. By using such a matrix,

Jan 1, 1959

By J. J. Hauser, H. C. Theuerer

A cathode sputtering technique is described which elin7inates the need for ultrahigh vacuum in preparing thin films of materials sensitive to gaseous impurities. This technique uses a fraction of the atoms sputtering within an anode container to getter actice gases, such as HzO, Oz, and Nz. The gases alzd gettering metal are deposited on the container walls, thus shielding the coating zone of the system from contamination. The use of the method for preparing superconducting-normal metal couples such as Ph-Cu and Ph-Pt is described, and the properties of the individual and composite films are given and discussed. GETTER sputtering is a method which greatly simplifies the preparation of thin films in cases where composition control is critical. A major difficulty with conventional sputtering and other vacuum-deposition techniques is the contamination of the forming film caused by residual gases, such as H20, CO, Oz, and Nz, in the coating equipment. The difficulty arises from the fact that even when the residual pressure in the system is as low as 1 x 10"6 Torr, with a deposition rate of 10A per sec, there are as many contaminating gas collisions with the substrate as there are with film-forming metallic atoms. It is not surprising, therefore, that with reactive metals, such as tantalum and niobium or with semiconductors, such as silicon and germanium, films with properties far different from the starting materials are obtained. In the case of niobium and tantalum, deposited either by sputtering or vacuum evaporation in systems with reactive gases at pressures of the order of 1 x l0-' Torr, the loss of superconductivity is traceable to interstial oxygen or nitrogen. On the other hand, working in vacuum of the order of 1 x l0-" Torr, Marchand and enema' have shown that superconducting films of tantalum with properties approaching those of bulk material are possible. At this level of gaseous impurities -lo6 metallic atoms arrive at the substrate before a contaminating collision occurs again assuming a deposition rate of 10A per sec. It is evident from the above that any successful vacuum technique requires the elimination of reactive gases from the region of the system where coating is occurring. Getter sputtering accomplishes this using conventional vacuum equipment with residual pressures in the 106 Torr range. In fact? vacuum systems with residual pressures of lo-" Torr are adequate for most purposes. With this method, sputtering is confined within an anode can and, by geometric design, sputtering itself is used to purify the argon at the lower and upper parts of the system by the gettering action of the reactive metal. In consequence, the central region of the system where coating occurs is shielded from gaseous contamination. Getter sputtering is particularly useful for the preparation of alloy and compound films. With this method, if a cathode of homogeneous composition is bombarded with high-energy argon ions, transfer of material to the substrate having the same composition as the cathode will occur. This is true after an initial equilibration time, even though the constituents of the cathode may have different sputtering rates. During equilibration, the surface of the cathode changes composition due to differences in sputtering rate, but mass conservation demands a steady-state condition such that the atoms sputtered from the surface have the same composition as the cathode material from which the surface is generated. GETTER-SPUTTERING APPARATUS The original form2 of the getter-sputtering apparatus is shown in Fig. 1. It consists of a closed nickel or stainless-steel can 4 in. tall and 2-3/8 in. in diameter. Mounted symmetrically from each end

Jan 1, 1965

MRS. SIDNEY J. JENNINGS, President MRS. ARTHUR S. DWIGHT, First Vice-President MRS. KARL EILERS, Second Vice-President MRS. H. W. HARDINGE, Third Vice-President MRS. BRADLEY STOUGHTON, Recording Secretary MRS. AXEL 0. IHLSENG, Corresponding Secretary MRS. HARRIS K. MASTERS, Treasurer Welfare Committee MRS. C. C, BURGER, Chairman Sub-Committees Americanization Belgian Relief MRS. LEVI HOLBROOK, Chairman MRS. HENRY H. KNOX, Chairman Emergency MRS. HERMAN A. PROSSER, Chairman A very successful meeting Of the Council of the Woman's Auxiliary was held Wednesday, July 18, and plans for war relief work were thoroughly discussed. The Belgian Relief Committee has sent out the following letter to the ten local sub-committees, which were formed to raise money to feed the Belgian children: "The Commission for Relief in Belgium announced in a letter from Mr. Hoover that after the first of June the United States Government would take over the relief of Belgium and Northern France and called attention to the following paragraph: ?Naturally, having built up such an effective organization you will desire to keep it alive as far as possible, and we venture to suggest that, although the general relief of the countries involved will now be met by the Government appropriations, emer-gencies and special conditions may arise which could only be met by private donations. In such circumstances your organization will afford a ready means of meeting the demands of the situation, whatever they may be. Should any of your contributors

Jan 9, 1917

By N. Plint, E. T. Pinkney

Copper segregation developments within the Anglo American Group are described with particular reference to the work of the TORCO Project Team. Some radical differences have been adopted in the mechan-ical approach as compared with methods used by previous workers. Most important among these are the following: (1) The heating unit is a fluidized-bed roaster. (2) A moving bed segregation chamber is used in which a packed bed of heated ore, to which reagents have been added, moves slowly downwards under gravity and is discharged at a controlled rate by means of a suitable valve mechanism. (3) The quantities of reagents used (sodium chloride and some form of carbon) are only a small fraction of those recommended by other investigators. (4) Retention times of only 2 min have been satisfactory for the complete segregation of many types of ore. Project TORCO is the code name given by Anglo American Corp. of South Africa, Ltd., to the investigation undertaken in Zambia to develop a plant capable of treating large tonnages of refractory copper-bearing ores by the segregation process. The process has now been under investigation for six years (1960-66) and during that period work has progressed from bench-scale laboratory tests through small-scale pilot-plant work to a 500-tpd commercial pilot unit. Test work has been carried out mainly on the ores of the Zambian Copperbelt and results have been encouraging. Recoveries on the order of 90% have been obtained on all Copperbelt ores tested with high concentrate grades. PRELIMINARY INVESTIGATION Laboratory scale segregation test work on Nchanga banded sandstone ore and oxidized ore from Kansan-shi was originally conducted by Professor Maurice Rey. SociCtC Miniere et Mktallurgique de Pefiarroya, in 1957. Both ores responded favorably to the process. In November, 1960, the consulting engineers of Anglo American Corp. of South Africa, Ltd., initiated preliminary investigations on the application of the segregation process to Copperbelt ores. In early laboratory work, samples were heated in a closed, externally heated tube furnace for one hour at temperatures ranging from 800 to 830°C. The free moisture content of the ore feed was 4% and reagent additions were 0.5% salt and 1.0% coal. Both salt and coal were pre-crushed to -48 mesh Tyler.* All samples except an ore from the Bancroft mine responded well to the process and recoveries of over 90% were obtained. The presence of dolomite was responsible for the relatively poor recoveries from the Bancroft ore, as tests on one of the other ores with additions of calcite or dolomite confirmed. Recoveries dropped from 94 to 45% Grades of all the rougher flotation concentrates produced were low at 10-15% copper. The laboratory investigation was then followed up on a pilot-plant scale. An attempt was made to carry out the segregation process in a coal-fired 5-ft-diam fluidized-bed roaster. The feed consisted of a banded sandstone from Nchanga to which 0.5% sodium chloride had been added. Reducing conditions were maintained in the roaster by the addition of coal in excess of that required for heating the feed. The excess coal and added salt constituted the segregation reagents and the temperature of the bed was held at approximately 750°C. Recoveries of copper and grades of concentrates were low. The reasons for lack of success were: (1) The reaction is a gaseous one and a fluidized-bed roaster is therefore unsuitable as a segregation unit. (2) Coal in excess of that required for heating was introduced into the fluidized bed and under these conditions some of the copper would be reduced in situ. The term "reduced in situ" is used here to describe any copper mineral reduced to the metallic state in its original site within the ore particles. If this copper is to be recovered by subsequent froth flotation it must first be liberated from the gangue by grinding or some other method which, in practice, is usually not feasible on ores of this type.

Jan 1, 1969

By F. H. Ellinger

TI HE crystal structure of neodymium has been re-A ported by Quill1 and by Klemm and Bommer"s to be hexagonal-close-packed, Strukturbericht-type A3, with a, = 3.650.4, c, = 5.890.4, c/a = 1.614. Klemm and Bommer,% owever, pointed out that the observed intensities of the lines of the neodymium powder pattern agreed only in part with the intensities calculated for the type A3 structure, and that the neodymium powder pattern showed extra lines which could not be traced to impurities. They found that these extra lines could be accounted for by doubling the c-axis, but apparently they did not consider their evidence to be sufficiently conclusive to justify reporting the doubled c-axis. In the present work, the structure of neodymium was found to be double hexagonal-close-packed. The neodymium metal used in the present investigation was obtained through the courtesy of F. H. Spedding of the Ames Laboratory. Its major impurity was stated to be 0.03 pct Ca. The author's spectrographic analysis indicated high purity and carbon was determined to be less than 30 ppm. X-ray powder specimens were prepared from filings stress relieved in vacuum at 200°C for 50 hr. Powder photographs were taken in an 114.6 mm diam camera (Straumanis film mounting) at room temperature and in a 19 cm diam Unicam high temperature camera at elevated temperatures. Copper x-radia-tion was used for all the photographs. The powder pattern of neodymium was found to index to a hexagonal unit cell with dimensions, as determined from the high angle Ka doublets, of: a.= 3.655+0.001.4; c, = 11.796+0.004.4; and c/a = 3.227 at room temperature. The measured density of neodymium shows that this cell contains 4 atoms, the calculated density is accordingly D, = 7.02 g per cu cm. The diffraction data for the first 15 lines of the powder pattern are listed in Table I. In a double hexagonal-close-packed unit cell, the 4 atoms would be in the positions (0,0,0), (0,0,%), (1/3, 2/3, 1/4), and (2/3,1/3,%) of space group P 6,/mmc. On the basis of these positions, the relative intensities of the reflections were calculated using the expression: 1+cos2 20 I oc \Frp 1 ' sin2 0 cos 0 where F is the structure factor and p is the multi- plicity factor. Since absorption was not taken into consideration, comparison of observed and calculated intensities should be made only for neighboring reflections. Each atom has 12 neighbors, 6 in the basal plane at a distance of 3.655.4 and 3 above and 3 below at the closer distance of 3.626.4. These distances correspond to an average radius of the neodymium atom of 1.820.4. The description of this structure in terms of A, B, and C close-packed layers of atoms is ABAC ABAC. ...... The structure repeats every fourth layer and the stacking sequence of the second, third, and fourth layers corresponds to cubic-close-packing of atoms. A series of powder photographs taken at successively increasing temperatures up to 680a10"C revealed that the double hexagonal-close-packed structure is stable up to this temperature. Acknowledgments The authw wishes to thank W. H. Zachariasen and A. S. Coffinberry for their helpful comments on this work and also Marion Gibbs for measuring the diffraction films. This work was sponsored by the United States Atomic Energy Commission.

Jan 1, 1956