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By O. N. Cole, R. E. Davis, T. D. Brotherton

Pvfoperties of rubidium and cesium are compared with those of other alkali metals. Methods for the preparation of rubidium and cesium metal are reviewed briefly, ad hazards and safety precautions required in handling rubidium and cesium metal are described. SimPle methods for handling laboratory quantities of elemental rubidium ad cesium under oil and under argon are illustrated. CESIUM and rubidium were both discovered by Bunsen and Kirchoff in the years 1860 and 1861. Cesium was discovered while Bunsen and Kirchoff were making a spectrographic study of spring water from Durkheim, Germany. It was the first element discovered by this technique. The element was given the Latin name "caesius" for sky blue because of the color it imparted to flames. Elemental cesium was first prepared by Setterberg in 1881 through electrolysis of a molten mixture of cesium and barium cyanides.' In 1861, Bunsen and Mirchoff discovered rubidium while making a spectrographic study of the alkali content of lepidolite ore from Saxony. Two prominent dark red lines appeared in the spectrum and so the element was named "rubidius" or dark red. In 1861 Bunsen and Kirchoff first prepared elemental rubidium through the electrolysis of molten rubidium chl~ride.~ The alkali metals are very similar in their chemical and physical properties. They are the most active metals, and all exhibit a single oxidation state of one. They are so reactive that they are never found in nature in the elemental state. The reactivity of he metals increases with atomic number. Rubidiurn and cesium ignite spontaneously in air and react explosively with water. This extreme reactivity makes necessary special equipment and techniques for the safe preparation and use of the metals. The cation: of Group IA can be separated from the metallic cations of other groups with relative ease, but the separation of the individual alkali cations is much more difficult because of their close chemical similarity. This close chemical and physical similarity of alkali metals can be inferred from the atomic radii, oxidation numbers, and ioni-zation potentials shown in Table I. A difficult but the most practical physical method of separating the elemental alkali metals from one another is by distillation. Only lithium has a boiling point sufficiently far-removed from the boiling points of the other alkali metals to make this method of separation feasible without elaborate and expensive equipment. This method is not used, however, for lithium because it possesses sufficient chemical dissimilarity from the other alkalies for it to be separated relatively easily as lithium hydroxide monohydrate or as lithium carbonate. Francium, the last member of the group, has no known stable isotopes. The naturally occurring

Jan 1, 1962

By I. R. Kramer

A delay time for yielding in cold-worked face-centered-cubic metals was found. Slip on (123) planes was observed. Glide on these planes occurred during the delay-time period before slip starts on the (111) planes. AN important approach to the study of the anchoring and blocking of dislocations is available through the delayed-yield phenomenon which has been observed in body-centered and hexagonal close-packed metal by several investigators. Clark and his associate1-5 showed that a delay time for yielding is present in mild steels and fine-grain molybdenum. Type 302 stainless, SAE 4130 normalized, SAE 4130 quenched and tempered, and 24s-T aluminum aid not have a delay time. Kramer and Maddin6 studied the delay-yield effect. in metal single crystals. While they found a delay time in body-centered-cubic metals none could be found in the face-centered-cubic metals. Later7 a delay time was found in hexagonal close-packed metals. cottrell8 has proposed an explanation for the difference in the yield phenomena of b.c.c. and f.c.c. metals based upon the anchoring of edge dislocations by the proper types of impurity atoms (C and N). In the body-centered-cubic lattice the interstitial atoms are near a cube edge and can interact with an edge dislocation, while in a face-centered-cubic lattice the distortion around an interstitial atom is of spherical symmetry and cannot anchor a screw dislocation which has practically no hydrostatic component. Cottrell's theory seems to account rather well for the behavior of body-centered-cubic . metals. EXPERIMENTAL PROCEDURE The apparatus used in these experiments is essentially of the same design as described previously.' Single crystals 1 in. long and having a diameter of % in. were placed in a pendulum which consisted of a bar 8 ft long designed with a crystal holder to accommodate the specimen at low temperatures. This portion of the apparatus was supported on fine molybdenum wires. A bar of the same diameter and length comprised the other portion of the apparatus. This bar was supported on a set of roller bearings arranged around the periphery of the bar to allow accurate alignment. This bar was propelled by means of a spring-loaded gun and allowed to strike the lead bar in front of the single-crystal specimen. SR-4 type A-8 resistance strain gages were cemented to the specimen and the strain measurements were obtained by amplifying the strain-gage output by means of a high-gain preamplifier. A tektronix 545 oscilloscope was used together with a polaroid camera to record the strain and time sweep. An Ellis Associate Bridge was used to calibrate the strain gages and calibration readings were obtained before each test. The sweep of the time signal was initiated by means of a miniature thyraton which was fired when the two bars came into contact. The single-crystal specimens were cut from single-crystal bars about 12 in. long, grown by a modified Bridgman technique. The aluminum crystals were made with material of 99.99 pct purity while the purity of the copper was 99.999 pct. A cut-off wheel was used to prepare the specimens which were then machined to the desired length. The two opposite faces of the specimen were parallel to each other and perpendicular to the axis of the specimen. The specimens were compressed 1 pct. No machining followed thereafter. In some cases prestraining was carried out in liquid nitrogen by impacting the specimens directly in the apparatus so that subsequent observations could be made without allowing the specimen to warm up to room temperature. The single crystals were compressed 1 pct at room temperature in a hand press without much control of the rate of deformation. In some cases specimens were recompressed to obtain the desired length change. As far as could be determined in these experiments this factor did not seem to influence the results. The SR-4 strain gages were glued with a cellulose type cement onto the specimen surface and baked at 45°C for 12 hr. As a check on the baking treatment gages were allowed to dry at room temperature. All delay time tests in this paper were conducted in a liquid nitrogen bath at -195°C. A schematic delay time oscilloscope trace is shown in Fig. 1. At point B the elastic stress wave caused by the impact reaches the strain gage on the specimen. The portion BC is the elastic strain. In this investigation the strain at point C was used to calculate the critical resolved shear stress by multiplying by the proper modulus depending upon the orientation of the single-crystal specimen. The time between C and D is the delay time portion of the curve. This portion of the curve is fairly flat but does have a definite microstrain associated with it. After the point D is reached the specimen deforms rapidly and the strain reaches a maximum at E. Following this, depending upon the length of the bar behind the specimen, the strain remains constant for a period and then decreases when the reflected elastic wave returns from the end of the pendulum bar. A permanent plastic strain is recorded on the oscilloscope trace and also measured by a strain-measuring bridge. The strain, E p,

Jan 1, 1960

By O. A. Cheadle, F. E. Lane

ThE computer program for arbitrary crystal systems reported by Camp and Clum' has been modified to make it more convenient for hexagonal crystals. The program' uses the Miller indexes (hkl) which can be confusing for hexagonal crystals while the modified program uses the Miller-Bravais indexes with four axes; e.g., the angles between the (110) planes, Fig. 1, are 0 and 90 deg but in the (hkil) system the angles between the (1150) planes are 0 and 60 deg. If a Laue photograph is taken of a crystal oriented with the prismatic planes nearly parallel to the film then the spots on the stereo graphic projection will be from high-index planes. The probable positions of the low-index planes, e.g., (0001) plane, can only be obtained from the intersection of zones and this is not accurate to 1 or 2 deg. The number of planes considered by the program (card 1)' has to be limited to the ones of low index or the program time is excessive but a solution will not be obtained if one of the spots has an index that is not being considered. To overcome this problem the program1 was modified so that if no fit was obtained at *1 deg (card 3) of the tabulated angles then ±2 or ±3 deg was tried. If still no solution was obtained either due to one of the angles not being measured correctly to ±3 deg or because one of the spots was from a high-index plane, then the last spot was discounted and a fit tried for the remaining spots at i1 deg, and so forth. The minimum number of spots that the program will try to fit is five. If the limit on any individual index is 4 (card 1) and (h + k + l + 1) is six then twenty-three planes are considered and there are over 1000 interplanar angles. Many pairs of planes have very similar interplanar angles and with the errors previously mentioned the program will often produce several alternative solutions to a group of spots particularly at ±2 or ±3 deg. However without the program the alternative solutions would probably not have been found. If a large number of spots are used the number of possible fits is reduced. In the example shown in Fig. 2, if only spots which are on the film are used (case 1) the program gives six possible solutions, Table I. However if points 7 and 8 are also used (case 2) the program gives only one fit which also agrees with a standard projection of the crystal. In addition to time-saving the program ensures that a correct solution is obtained since it is unlikely that all the alternatives would have been gound manually; the first would probably be assumed to be the correct solution. The program has been used for zirconium crystals but is equally suitable for other hexagonal materials.

Jan 1, 1969

By John Birkinbine

" Whether an iron-ore should be roasted is a question which very seldom arises ; at least, this question seldom ought to arise. With the exception of the red impalpable oxide, the whole series of ironores require roasting—even the specular iron-ore, if it is very compact—but the best oxide, if too compact, works badly in the furnace. All other ores should be subjected to calcination. Some ironmasters are in the habit of using the hydrates raw, but this should riot be done where clay-ores are smelted or where the hydrates contain either chlorides or phosphates. But in the latter case, the pig metal will be cold-short if there is too much phosphorus. Under all circumstances, however, it is best to roast the ores if we expect good metal and well-regulated furnace operations. " The object of roasting ores is to produce higher oxidation and to expel injurious admixtures. In both cases liberal access of atmospheric air is required ; we should, therefore, so arrange our roasting operations as to fulfil these conditions, from which it will appear that different ores require different treatment."* The above may be considered an extreme, and perhaps erroneous view; but there is no question as to the absence of a general appreciation concerning the value of preparing ores of iron for smelting in the blast-furnace.

Jan 1, 1884

By J. B. Clark

In multiphase ternary diffusion studies, plots of the variation bf the composition on the isotherm constitutes one of the most effective methods of presenting experimental results, especially if such plots are made in a manner which relates the composition path on the isotherm with the diffusion layer structure in the couple. Unfortunately, if different conventions for plotting are used serious misinterpretations occur readily, causing apparent disagreement between investigators who actually share the same viewpoint. A common convention for mapping these diffusion paths is needed at this time because with the increasing use of the electron-probe X-ray microanalyzer, a much greater number of ternary diffusion studies can be expected in the near future. In an effort to prevent unnecessary confusion in the future litera- ture, a convention for these plots is proposed, as outlined below. A hypothetical example of the use of these conventions is given in Fig. 1 where the path of composition through the diffusion structure of the 100 pct A/50 pct B, 50 pct C couple is plotted on the appropriate isotherm of the ABC system. The lower case letters relate the region in the diffusion layer structure to the appropriate composition on the ternary isotherm. 1) The diffusion path is plotted on the isothermal section corresponding to the diffusion temperature of the couple. 2) The terminal compositions of the plotted diffusion path are the initial compositions of the couple halves—provided infinite boundary conditions are maintained. If, in either couple half, infinite conditions are not maintained, then the path terminates at the composition of the exterior surface of the couple. If, at this surface, the composition varies with time or if the plotted path is time dependent, then the diffusion time should be noted beside the plotted path. 3) A solid line crossing a single phase field (e.g., line a-b in Fig. 1) denotes an existing layer of that phase in the diffused couple. 4) A dashed line crossing a two-phase field parallel to the tie lines (e.g., line g-h) represents an interface between the two phases with interfacial compositions designated by the ends of the tie-line. The line represents no spatial extent. 5) A solid line crossing a two-phase field so as to cut tie lines (e.g., line b-c or line j-k) represents a locally equilibrated columnar two-phase layer. The solid line should cut those tie lines which correspond to the lateral interfacial equilibria along the columnar

Jan 1, 1963

By N. Malakouti, R. H. Whipp, O. A. Kuby, R. M. Smailer

A detailed description of the development of the FIOR process (Brown, Campbell, and Saxon, 1966) and, subsequently, other technical papers related to the operation and start up of the FIOR plant (Violetta, 1975; Whipp, 1980) are available in the technical literature. The Fluidized Iron Ore Reduction (FIOR) process plant constructed in the Matanzas region of Venezuela represents the first commercial application of this technology. The FIOR process was developed by Exxon Co. during the 1950s and 1960s. The facility in Venezuela was designed and constructed by Davy McKee, with plant start-up in 1976. While there is a minority government ownership in the company, FIOR de Venezuela operates as a private sector company with the majority of ownership being private capital. The FIOR process is well suited to utilize the naturally occurring iron ore fines of the Cerro Bolivar and San Isidro iron ore deposits located less than 100 km (62 miles) south of the plant site. Availability of natural gas within 150 km (93 miles) to the north, and a location bordering on the confluence of the Caroni and the Orinoco Rivers makes for an ideal geographic site. Feed stock to the FIOR plant consists of naturally occurring iron ore fines from these ore bodies, which are screened to -6mm (-0.2 in.) prior to drying in the ore preparation plant. A simplified flow plan is shown in [Fig. 1]. The dried ore is then transferred to the top of a structure containing four fluid-bed reactors located above one another so the mineral may flow from one reactor to the next by gravity. A reducing gas containing 90% hydrogen is made by steam reforming of natural gas, a CO shift

Jan 1, 1983

By C. W. MacGregor

In the testing of materials there exist various methods of recording graphically the behavior of a material subjected to tensile stress. Probably the most common method is to plot the tensile stress So, obtained by dividing the load P by the original area of cross section A0 at the start of the test, as a function of the strain e0, which is obtained by dividing the ?Lo or the change in the gauge length by the original gauge length Lo. A list of the symbols used here is given in Table 1. This method, while it has proved useful in the routine testing and comparison of various materials, does not have a very sound physical basis, as was first pointed out by P. Ludwikl, and consequently does not afford a very deep insight into the true physical behavior of the material under stress. Among the objections to this method may be mentioned: (1) that by dividing the load P at any stage of the test by the original area A. a fictitious stress is obtained, which does not actually exist; (2) that the strain e0 = ?L0 is not an exact expression for the true strain for large values of ?LO in per cent of Lo; (3) that when necking starts the strain varies considerably along the gauge length and the above expression no longer gives the true strain existing at any point on the outside of the bar; and (4) that the axial strain varies over the cross section of the necked portion and e0 does not represent an average of these strains over the cross section. Stresses taken from such a diagram would be only approximate and, if used to compare results of a test on a given material under simple tension with results obtained under combined stresses, certain errors would be thus introduced. In order to overcome some of these objections, various methods have been suggested, both as to the quantities to be measured and as to their graphical representation. In some cases the so-called "true stress," obtained by dividing the load P by the actual area of cross section A existing when the load P was applied, is plotted as a function of the strain

Jan 1, 1937

By E. Martinez, M. L. Hollander

Sulfurization of copper oxides was investigated using differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). When mixtures of cuprous oxide and sulfur were heated, the surface of the cuprous oxide was converted to cupric sulfide at the melting point of sulfur (119°C); additional sulfuriza-tion took place when the sulfur vaporized above 200°C. Cupric oxide also reacted with sulfur to form cupric sulfide but the starting temperature was approximtely 225°C. When the cupric oxide and sulfur were physically separated, sulfurization still occurred indicating a reaction with the vapor phase of sulfur. Sulfurization was obtained in runs with cuprite, chrysocolla and basic copper carbonate. Further decomposition of cupric to cuprous sulfide was noted at somewhat higher temperatures. The DTA-TGA data made it possible to set up postulated reactions in each system. These techniques were found to be well suited for studies of this type. Because of the difficulty encountered in flotation of many metallic oxide minerals, efforts have been made to find suitable reagent combinations to sulfi-dize these minerals in the flotation circuit. Recently Bautista and Sollenberger,1 using a different approach, showed that the surfaces of many oxide minerals can be converted to sulfides by heating them with sulfur to temperatures between 150° and 225°C. This technique was effective even with chrysocolla, a mineral which is very difficult to sulfidize. The primary objective of the present study was to obtain information on the reactions between the oxide minerals and suIfur. A better understanding of the mechanisms involved might prove useful in pointing the way to improvements in the process. A secondary objective was to demonstrate the value of thermo-analysis in investigations of this type. Bollin and Kerr2 have reported the use of a modification of differential thermal analysis to study the thermal reactions which occur on heating elemental constituents in a closed system to synthesize copper sulfides and iron sulfides. Differential thermal analysis (DTA) was used to detect enthalpic changes as mixtures of minerals and sulfur were heated. The DTA indicated the temperatures at which reactions started and whether they were exothermic or endothermic. Weight change data were obtained by thermal gravimetric analysis (TGA). These data could often be used to support postulated reactions and to eliminate consideration of other possible reactions. EQUlPMENT Differential thermal analysis (DTA) involves measuring the temperature difference between the sample being tested and a thermally inert reference, generally aluminum oxide, as both are heated at a uniform rate. Series connected thermocouples in the sample and reference are used to detect the temperature differences that occur as the sample undergoes enthalpic changes.3 Crystalline transitions, fusions, vaporizations, dehydrations, decompositions and many solid state reactions can be detected. A DTA unit manufactured by the Robert L. Stone Co., Austin, Tex., was used in this investigation with a temperature rate increase of 10°C per min. The samples and reference were placed in Inconel cups with wells in the bottom into which the differential thermocouples fit, and run in a nitrogen atmosphere. Thermal gravimetric analysis (TGA) measures the changes in weight that a sample undergoes as it is heated. A Chevenard thermobalance converted electronically for graphic recording was used with a heating rate of 5°C per minute. An X-Y recorder plotted temperature on the X axis and weight changes on the Y axis. A flow of 250 ml per min of nitrogen was streamed through the furnace. Samples were placed in a porcelain crucible open at the top, unless otherwise noted. EXPERIMENTAL RESULTS Sulfur: Two sulfur samples from different sources were tested. The DTA of a high purity sulfur and a reagent grade sublimed sulfur are shown in Fig. 1. Nearly all the tests were run with the sublimed sulfur due to the difficulty in grinding and high electrostatic charge encountered with the high purity sample. Sulfur undergoes three endothermal reactions below 200°C. The first is a solid-solid crystalline transi-

Jan 1, 1964

By E. I. Larsen, E. F. Swazy, F. R. Hensel

Experience has indicated that hard bronzes are not suitable for bearing applications where high bearing loads and speeds are involved. It is the general practice to utilize softer materials for these purposes, such as copper, lead, silver, babbitt, lead-base alloys, and more recently aluminum-base alloys, preferably supported by a steel backing. It was the objective of the present investigation to study a new material produced by powder metallurgical methods susceptible to precipitation-hardening. Test MAteriaIs Preliminary tests were made with compacts containing copper, nickel and silicon in quantities sufficient to form 3 to 5 per cent nickel silicide. It mas found that this type of alloy was susceptible to the formation of a soft surface shell when sintered in tank hydrogen. The depth of the shell depended On the length of sintering time and sintering temperature, and varied in thickness from a few thousandths to as much as One eighth inch. This soft shell resulted from the preferential oxidation of silicon, thereby reducing the efficiency of age-hardening by the nickel silicide compound. The body of the sintered compacts below the soft shell could be precipitation-hardened to a hardness of 70 to 85 Rockwell B, by quenching from goo°C. and age-hardening at 450°C. A series of tests was made with various addition agents, in order to decrease the rate of preferential oxidation, and it was found that phosphorus was most beneficial in this respect. After considerable experimentation, the following nominal com-position was accepted as standard: 2.4 per cent nickel; 0.8 silicon; 0.3 phosphorus; balance copper. The physical propertties and certain bearing properties of this alloy are described in the present paper Preparation of Compacts Several methods of incorporating the hardening ingredient (nickel silicide) were studied. Compacts formed from copper, nickel and silicon powders were found to be inferior to those fabricated from prealloyed nickel silicide master alloys, because of the rapid oxidation of pure silicon during sintering. The use of a prealloyed nickel silicide hardener containing 25 per cent silicon and 75 per cent nickel could be further improved by preparing a master alloy, incorporating nickel, silicon, phosphorus and copper, having the following nominal composition~ 25 per cent nickel; 7 silicon; 3 phosphorus 64 copper. This alloy is brittle in the cast condition and can be readily powdered. Sintering Procedure The blended powders were pressed at '5 to 40 tons per sq' in., the pressure depending on the size and shape of the compacts. Sintering was carried out in hydrogen or cracked ammonia atmospheres at

Jan 1, 1946

By E. I. Larsen, E. F. Swazy, F. R. Hensel

Experience has indicated that hard bronzes are not suitable for bearing applications where high bearing loads and speeds are involved. It is the general practice to utilize softer materials for these purposes, such as copper, lead, silver, babbitt, lead-base alloys, and more recently aluminum-base alloys, preferably supported by a steel backing. It was the objective of the present investigation to study a new material produced by powder metallurgical methods susceptible to precipitation-hardening. Test MAteriaIs Preliminary tests were made with compacts containing copper, nickel and silicon in quantities sufficient to form 3 to 5 per cent nickel silicide. It mas found that this type of alloy was susceptible to the formation of a soft surface shell when sintered in tank hydrogen. The depth of the shell depended On the length of sintering time and sintering temperature, and varied in thickness from a few thousandths to as much as One eighth inch. This soft shell resulted from the preferential oxidation of silicon, thereby reducing the efficiency of age-hardening by the nickel silicide compound. The body of the sintered compacts below the soft shell could be precipitation-hardened to a hardness of 70 to 85 Rockwell B, by quenching from goo°C. and age-hardening at 450°C. A series of tests was made with various addition agents, in order to decrease the rate of preferential oxidation, and it was found that phosphorus was most beneficial in this respect. After considerable experimentation, the following nominal com-position was accepted as standard: 2.4 per cent nickel; 0.8 silicon; 0.3 phosphorus; balance copper. The physical propertties and certain bearing properties of this alloy are described in the present paper Preparation of Compacts Several methods of incorporating the hardening ingredient (nickel silicide) were studied. Compacts formed from copper, nickel and silicon powders were found to be inferior to those fabricated from prealloyed nickel silicide master alloys, because of the rapid oxidation of pure silicon during sintering. The use of a prealloyed nickel silicide hardener containing 25 per cent silicon and 75 per cent nickel could be further improved by preparing a master alloy, incorporating nickel, silicon, phosphorus and copper, having the following nominal composition~ 25 per cent nickel; 7 silicon; 3 phosphorus 64 copper. This alloy is brittle in the cast condition and can be readily powdered. Sintering Procedure The blended powders were pressed at '5 to 40 tons per sq' in., the pressure depending on the size and shape of the compacts. Sintering was carried out in hydrogen or cracked ammonia atmospheres at

Jan 1, 1946

By J. B. Murdoch, John G. Jackson

The many mechanical, geological, and economic factors which influence the planning of a directional drilling program are thoroughly discussed and analyzed. It is demonstrated that the planning of a directionally drilled multiple-well artificial island location is a complicated undertaking and that it is imperative that complete planning and engineering analysis be undertaken before the program is started. Complete planning is profitable because all of the factors influencing the directional work are in general interrelated and many time compromises have to be made before a harmonious program results. The engineering control necessary to accomplish a complicated directional drilling program is outlined. Various means by which engineering control can be increased, such as cylinder drilling specifications, are given. A hypothetical example is developed for a complete offshore artificial island of ten wells to demonstrate the more important factors involved in the planning. Included with this example are special charts and tables which make more rapid the drafting of directional drilling proposals and maps. Introduction A petroleum engineer must consider many and varied factors when planning a long range directional drilling program for an offshore or inaccessible location on an oil structure. The basic principles of direc- tional drilling planning and operation must be reconciled with his company's drilling practices, and frequently special concessions to standard drilling and production practices should be made. The field techniques and tools used in directional drilling are well known and widely used, but the deliberate, careful planning of a complete directional program is in the main a recent innovation. This development, plus the increased demand for oil resources and the consequent exploitation of inaccessible structures and offshore locations, has placed this problem before many engineering departments for the first time. Directional drilling programs of a very complex and difficult nature have been successfully carried out in the Mid-Continent and Pacific Coast regions. The planning itself of a directional drilling project, however, has not had the careful analysis it deserves and we can reasonably expect widespread future progress along thesc lines. Data and experience gained in these programs by the directional drilling service companies and the oil producers have been studied with the objective of giving the engineer a better conception of the factors which govern the various steps in planning a series of directional wells. The newest engineering procedures are the result of recent careful analysis of years of directional drilling work accomplished under the supervision of directional drilling service companies working with the oil companies. The purpose of this paper is to illustrate

Jan 1, 1949

By Arthur Phillips

THE study of anisotropy in metals has been greatly stimulated in recent years by the rapid development of X-ray methods for determining the crystallographic relationships of wrought and annealed materials. Prior to this time the knowledge regarding the directional properties of commercial alloys consisted almost exclusively of observations of a practical nature made during the fabrication of metal objects, supplemented by a limited number of mechanical tests on specimens cut at various angles to the direction of working. Such observations clearly indicate that the common methods of cold-working metals cause both a crystallographic and a mechanical fibering varying in character and degree according to the nature and extent of the deforming process. Even after annealing, following certain not too well known combinations of reductions and anneals, a preferred orientation may exist, thereby constituting a residual fiber effect sufficiently pronounced to manifest directional properties. With the application of the X-ray the experimental horizon was extended chiefly because the study of anisotropic metals promised to offer direct and quantitative evidence regarding the involved mechanism of fragmentation and plastic flow. As a natural consequence the intensive studies in this direction have yielded a vast accumulation of data of ultimate potential value. Unfortunately, however, as is commonly the case in entering a virgin field of experimentation, many of the data cannot be molded into complete and coherent form because of the many unrelated conditions of the experimental projects. Again, the results of the study of single crystals have been rather naturally but at times indiscriminately applied to polycrystalline metals. Furthermore, sweeping statements have been made regarding the behavior during working and annealing of metals and alloys, entirely on the basis of similarity in lattice arrangement. There is abundant reason for believing that relatively small concentration variables, differences, in magnitude and distribution of applied stresses, and the character of associated annealing treatments may in some cases greatly influence the mechanics of flow and consequently largely determine the final structural characteristics of the metal.

Jan 1, 1932

By R. L. Perrine

A stability theory is developed for miscible liquid-liquid displacement within a porous medium. In the usual case considered, a high-density high-viscosity "oil" is displaced downdip by a low-density low-viscosity "solvent'! Perturbation methods are used to find the conditions under which the spreading mechanism changes from the stable dispersion process to unstable viscous fingering. We find that instability is conditional, that there is a dependence on the shape of a disturbance leading to a"diameter" effect and that very difficult experimental scaling problems may result. A useful consequence is the definition of a minimum "slug size" for stable miscible displacement. This should make possible optimum use of the solvent process for oil recovery. The results may apply to many situations in which one fluid displaces another of somewhat different fluid properties within a porous medium. INTRODUCTION The process of miscible liquid-liquid displacement looked very favorable when it first received serious consideration as a means to increase petroleum recovery. Some early laboratory results were interpreted to mean that only a small "slug" of solvent was needed, perhaps 2 to 3 per cent of a hydrocarbon pore volume. This "slug" could recover the oil in an entire reservoir provided the fluids remained miscible.1,2 Only a slow growth of the "mixing zone", or gradual transition from oil to solvent, should occur. This would follow naturally from mixing by a dispersion mechanism such as that described by Scheidegger.3 And, indeed, laboratory cores have shown this kind of behavior provided solvent viscosity was at least as great as that of the oi1.2,4-6 The same kind of behavior has also been observed with solvent viscosity lower than that of the oil after the distance traversed became large. Not all laboratory results have been this favorable, however.7-9 Mixing zone growth may become proportional to the distance traveled rather than the square root of this quantity. Such behavior accompanies high rates in short systems of large diameter, provided the viscosity ratio is adverse. If this more rapid spreading were to persist in a reservoir, the solvent requirement for miscible "slug" displacement could exceed 30 per cent of a pore volume. There is considerable economic importance in the difference between 3 and 30 per cent solvent. A 1ogical conclusion is that two different kinds of flow behavior are possible, with each kind leading to a different result. One kind gives efficient displacement, the other does not. In the efficient case, the solvent bank spreads out only by the mechanism we have termed dispersion. Under these conditions, displacement is as near piston-like as possible. In the second kind of flow, found only with adverse viscosity ratios, viscous fingering occurs. That is, permeability variations cause a small finger of low-viscosity solvent-rich fluid to move ahead of its average position within the mixing zone. This creates a path of low resistance to flow, and an even greater amount of solvent-rich fluid follows. Thus, the process is autocatalytic. Once started, the fingering mechanism rapidly becomes dominant. The question to be answered is this. Under what conditions will each of these two different kinds of flow occur? In particular, what conditions denote the transition from dispersion to viscous fingering as the solvent spreading mechanism? The answer may tell us whether or not the desirable, near piston-like miscible displacement process is practical. An answer to this problem can be obtained from theory by the use of perturbation methods. The procedure is as follows. We first formulate a mathematical representation of the system. Then a small disturbance (or perturbation) in solvent concentration profile is introduced and observed to see what happens. Unstable flow is indicated when a small disturbance will grow larger. This will lead to eventual viscous fingering. If on the other hand the disturbance dies out, the displacement is stable. In this latter case, with dispersion as the spreading mechanism, near piston-like displacement is possible. Thus, this paper presents the development of a stability theory for miscible liquid-liquid displace-

By E. O. Wagner, V. F. Parry, W. S. Landers

Development work has shown that the yield of primary tar from coal is proportional to the heat in the volatile matter of the coal and that the yield of tar from noncoking coals may vary from 10 to 45 gal per ton on the ash-free and moisture-free basis. Pilot plant operations have proved that 100 to 135 pct of the bench-scale carbonization-assay yield of tar can be obtained. FOLLOWING investigations by the Denver Bureau of Mines on drying fine coal in the entrained state,'. ' Texas Power & Light Co. employed the fluidized technique to upgrade Texas lignite for use in power plants. Because of the rapidly rising cost of natural gas in Texas the company agreed to cooperate with the Bureau of Mines in studying further the upgrading of lignite by low-temperature carbonization, since potential value of the tar would help offset the cost of fuel. Considerable interest was aroused, therefore, when Aluminum Co. of America decided to use dried lignite in its 240,000-kw power plant at Rockdale, Texas, operated by Texas Power & Light. Carbonization of coal before burning in a power plant is not new. Plants in Germany have been operated for many years on carbonized brown coal and lignite briquets produced in large integrated plants. Large-scale experiments in carbonizing pulverized coal with hot flue gases were made 30 years ago at Milwaukee," and many inventors have proposed other processes. In the U. S., technical and economic problems have prevented successful operation of large plants on carbonized coal. but new techniques of handling solids in fluidized beds may overcome these difficulties, particularly if the higher volatile noncoking coals are used. Any bituminous material will decompose when heated to about 900°F to yield primary tar, gas, and char. The quantity of tar obtained from various coals depends on their rank and volatile content and to some extent on rate and method of heating. The liquid products derived from thermal decomposition of peat, brown coal. lignites, oil shale, and noncoking bituminous coals can be easily liberated by rapidly heating these materials in a fluidized bed at about 500°C (932°F). Since it takes only a few minutes to heat small particles of fuel to carbonizing temperature in a fluidized bed, processing plants can be built to handle up to 50 tph at relatively low cost. The pioneering development work being conducted at Rockdale, Texas, by Alcoa and Texas Power & Light will solve many engineering problems of such operations. The Bureau of Mines at Denver has studied the carbonizing properties of several hundred coals by small scale assay at 500°C, deriving a simple correlation between the potential yield of tar and the proximate analysis. This correlation, shown in Fig. 1, compares the heat in the volatile matter of the coal with the potential yield of primary tar. The yield of primary tar varies from 12 to 50 gal per ton of pure coal." About the same amount of heat is needed to * MAF equals moisture-and-ash-free basis. distil any dry coal at 500°C, and the time required to carbonize a given particle size is about the same for any coal. It is therefore obvious that coals rich in volatile matter will show the greatest profits when processed. Texas lignites are rich in volatile matter, which contributes some 5700 Btu per lb of MAF coal, and the potential primary tar and oil yield from this lignite averages 12 pct by weight or 27 gal per ton from the pure lignite. Texas lignites are considerably richer in potential tar than lignites of North Dakota and Montana. During 1950 the Bureau of Mines conducted many experiments on carbonizing fine dry coal in the entrained state, publishing a report4 n major features of pilot and commercial-size units required to carry out the process. Additional experimental work has been done at Denver and the pilot plant has been improved, particularly the facilities for studying removal of fine dusts from tar vapors and gases at high temperatures by electrostatic precipitation. A number of materials have been carbonized, including sawdust, peat, brown coal, Brazilian oil shale, lignites, and the lower rank bituminous coals having noncoking properties. Straight coking coals cannot

Jan 1, 1957

By W. A. Griffith

Fractional replication of factorial design, a general method for planning experimentation and for analysis of data obtained, is described as applied to a flotation investigation. This method leads to determination of optimum process conditions with minimum experimental effort. Its advantages over simple factorial design are demonstrated. A METHOD for planning experimentation and for analyzing the data secured will be demonstrated. This method, termed fractional replication of factorial design, employs a relatively small number of individual experiments to determine which of a large number of process variables are controlling, to determine which combination of levels of these variables is most likely to produce optimum results, and also to predict what results will be obtained with a particular combination of conditions not already tested. Although the general method is not new, having been developed by Finney in 1945,' the extent to which it can improve the effectiveness of applied research generally has not been recognized by metallurgists. The fractional replication procedure is particularly useful in flotation experimentation and an example from such an investigation will be used in the paper. However, it has equal value in any investigation in which similar experimental difficulties are encountered. In developing a flotation process for a particular mineral separation, the investigator is inevitably confronted with the following difficulties: 1—There are a large number of potentially important process variables. 2—Results of individual experiments are not highly reproducible, due in part to the difficulty in precisely controlling all the variables. 3—Considerable effort is expended in conducting individual experiments. 4—There are practical limits on the number of individual experiments which can be made. In situations of just such a type, modern statistical methods of planning experimentation and analyzing data have their greatest value. Applications of one such technique, called factorial design, to problems of this type have been described by Dorenfeld and others.'-' The simple factorial design is an efficient procedure when the investigator hopes to provide a comprehensive understanding of the effects and interrelationships of a small number of variables over a limited range. In applied research, this is seldom the main objective. Rather, the investigator usually wishes to determine which of the many potentially important variables are in fact controlling, which levels of the controlling variables will provide opti- mum metallurgical results, and what these results will be at optimum conditions. Interest in detailed trends is limited to the controlling variables and to levels in the region of optimum conditions. Simple factorial design has serious deficiencies for such objectives and is not the most efficient method of experimental design. Deficiencies of Factorial Design In a simple factorial design, an experiment must be made at every possible combination of each level of every variable, once these have been chosen and the levels of each to be included have been decided upon. As the number of variables or levels of each increases, the experimental program quickly reaches prohibitive size. For example, an investigation of only four variables, each at four levels, requires 256 individual experiments. Often upon completion of such an extensive program, it is found that one or more of the variables has metallurgically unimportant effects or that a poor estimate has been made as to the appropriate range of levels to be investigated. The result is that only a small proportion of the data obtained falls in the range of real metallurgical interest. Indeed, it frequently can be anticipated that certain combinations of levels of variables will not produce results of interest, but they still must be included so that the essential balance, or orthogonality, of the design will be retained. It may be true that factorial design will provide the greatest amount of information from a given number of experiments, but it does not necessarily follow that it will lead to the desired information with a minimum number of experiments. Much of the information provided may be of little value. Advantages of Fractional Replication The disadvantages of simple factorial design are overcome to a great extent by a modification known as fractional replication. This is a technique for sampling systematically the potential data of a full factorial experiment, that is, the data which would have been obtained if the complete factorially designed program had been completed. Only a fraction of the total array of experiments is made, but the experiments are chosen in such a way that the important advantages of factorial design and the accompanying analysis of variance are retained. The data obtained from the first group of experiments are used to determine which of several variables are controlling and which levels of these variables are most likely to produce the desired result. Unimportant variables and levels of variables then may be

Jan 1, 1956

By John M. Hartman

On May 19th, 1857, an English patent was granted to E. A. Cowper for heating air or other gases under pressure by means of a regenerator inclosed in an air-tight iron case, having between the regenerator and case a lining of brick. This patent provided for heating the stoves by a separate fireplace, or by gas direct from the blast furnace. A number of forms of interior arrangement of the brickwork are shown in the drawings; also hollow poppet valves with hollow stems, and a pipe inside of the stem for circulating the water; the valve seats have coil cast in them for water circulation to keep them cool; slide valves, with snake coil cast in the discs, are shown, and the use of cold air for cooling the valves is also described. The combustion-chamber of these stoves was central, and openings mere provided at the top and bottom to get into the stoves. These Cowper stoves are all circular in section. November loth, 1865, an English patent was granted to Thomas Whitwell for regenerative stoves for heating air or gas, provided with cleaning openings at the top and bottom capable of being closed with firebrick plugs and doors. The drawings show a rectangular stove inclosed in an iron case. The interior brickwork has numerous upand-down passages through the stove, but there is no claim on the interior construction. March 3d, 1868, an English patent was granted to Charles Cochrane for a slide valve to be subjected to high heats. The disc of this valve was hollow, and had a circulation of water through it by the two hollow stems that operated it. The valve-seat was detachable and had a coil cast in it, through which water circulated. The valve and seat were placed on an incline to the body to cause the valve-disc to lie on the valve-seat. A cap was placed on the bottom of the body to get at the interior readily. January 5th, 1870, an English patent was granted to Siemens, Cowper and Cochrane for the construction of regenerators in firebrick stoves, with numerous vertical passages of sufficient size to allow a brush to pass through and clean them. These passages had slight projections on the sides to tarn the air over and over as it passed through. A claim also covered the use of horizontal passages connected at each end alternately, and the use of blasts or jets of air,

Jan 1, 1880

By Joan M. Hartman

ON May 19th, 1857, an English patent was granted to E. A. Cowper for heating air or other gases under pressure by means of a regenerator inclosed in an air-tight iron case, having between the regenerator and case a lining of brick. This patent provided for heating the stoves by a separate fireplace, or by gas direct from the blast furnace. A number of forms of interior arrangement of the brickwork are shown in the drawings; also hollow poppet valves with hollow stems, and a pipe inside of the stem for circulating the water; the valve seats have coil cast in them for water circulation to keep them cool; slide valves, with snake coil cast in the discs, are shown, and the use of cold air for cooling the valves is also described. The combustion-chamber of these stoves was central, and openings were provided at the top and bottom to get into the stoves. These Cowper stoves are all circular in section. November 10th, 1865, an English patent was granted to Thomas Whitwell for regenerative stoves for heating air or gas, provided with cleaning openings at the top and bottom capable of being closed with firebrick plugs and doors. The drawings show a rectangular stove inclosed in an iron case. The interior brickwork has numerous up-and-down passages through the stove, but there is no claim on the interior construction. March 3d, 1868, an English patent was granted to Charles Cochrane for a slide valve to be subjected to high heats. The disc of this valve was hollow, and had a circulation of water through it by the two hollow steins that operated it. The valve-seat was detachable and had a coil cast in it, through which water circulated. The valve and seat were placed on an incline to the body to cause the valve-disc to lie on the valve-seat. A cap was placed on the bottom of the body to get at the interior readily. January 5th, 1870, an English patent was granted to Siemens, Cowper and Cochrane for the construction of regenerators in fire-brick stoves, with numerous vertical passages of sufficient size to allow a brush to pass through and clean them. These passages had slight projections on the sides to turn the air over and over as it passed through. A claim also covered the use of horizontal passages connected at each end alternately, and the use of blasts or jets of air,

Jan 1, 1880

By G. R. M. Del Giudice, A. F. Taggart, Othon A. Ziehl

In a previous paper1 in which one of the authors collaborated, it was postulated that All dissolved reagents which, in flotation pulps, either by action on the to-be-floated or on the not-to-be-floated particles affect their floatability, junction by reason of chemical reactions of well recognized types between the reagent and the particle affected. This generalization, apparently, like many pioneer structures, had for certain observers a flimsy appearance, and these, judging its stability rather by the number than by the character of its foundation posts, have attempted variously to overthrow it, either by the frontal attack of general denial, or by the flanking movement involved in assuming that those cases in which the facts were unknown or unproved were, therefore, discordant. But as time has passed and further evidence on the question has accumulated, it has become apparent that the results of verifiable experiments add stone by stone to the substructure of the hypothesis, and that the super-tructure has lost nothing in weathering. The present paper constitutes an examination of the opposing positions in the light of the more recent evidence developed. It will clarify the discussion if, at this point, we state more fully the implications of the disputed hypothesis. In the first place, it is explicitly limited to reagents that are dissolved in the water of the flotation pulp. Next, it refers only to such of these dissolved reagents as act on the solid particles in the pulp to affect their floatability. This includes the collectors, activators, and certain depressors and gangue-control reagrnts, but not the pure frothers, and not, necessarily, conditioners whose function seems to be merely that of pH control, although in certain cases it has been demonstrated that such control has the effect of regulating the primary reaction of the collector, depressor, or the like. Finally, there is no limitation as to the nature of the chemical reaction postulated.

Jan 1, 1935

By AIME AIME

AMONG the recent mining and metallurgical developments in England great interest has been shown in the development of an iron-ore field covering 26,0.00 acres in Northamptonshire, containing 500,¬000,000 long tons of ore; and the erection at Corby, by Stewarts & Lloyds, of a modern basic bessemer steel plant and tube works. The entire project was planned to cost about £3,300,000. Many improvements have been made in the varied equipment that is being installed, some of which has set mew records for massiveness. There is, for instance, a new roll crusher, which has been manufactured by Hadfields, Limited, of Sheffield, the largest ever built in England, and weighing 130 tons. This machine, shown in Fig. 1, as erected at the Hadfields shops, is primarily designed to take blocks of iron ore as they come from the steam shovel. The maximum size is 54 by 48 by 36 in., hut occasional pieces slightly larger than this may be accommodated. The capacity is upwards of 500 tons per hour, the product passing to a secon-

Jan 1, 1934

By H. M. Chance

The Choctaw coal-field is a direct westward extension of the Arkansas coal-field, but its coals are not like Arkansas coals, except in the country immediately adjoining the Arkansas line. From the base of the coal-bearing rocks up to the top of the coalmeasures, I find a total thickness of at least 8500 feet. This great mass of coal-bearing rocks consists of an alternation of slates, shales, sandstones and coal-beds, with their accompanying under-beds of fire-clay. Only one small bed of limestone was observed. This occurs near the middle of the series; it is about eighteen inches thick, and quite arenaceous. The formation is naturally subdivided by seven or eight thick beds of sandstone, varying from 50 to 200 feet in thickness, the outcropping edges of which form a series of more or less bold " hogback " ridges, the interbedded shales and slate forming the intervening valleys. The base of the coal-series is a massive sandstone, ranging from 100 to 200 feet or more in thickness, lying immediately beneath the Grady coal-bed, which is the lowest known coal. In the district embraced between. the Missouri, Kansas and Texas railroad and the Arkansas State line, this sand-rock usually forms a bold semi-mountainous ridge. This is the ridge through which the St. Louis and San Francisco railroad passes at Bryan station, where the Grady coal-bed is opened and worked, from which point it can be traced westward without difficulty, passing about three miles north of Le Flor on the same railroad, thence west to the " Little Narrows " (which is merely a gap in the ridge), 'and beyond to a point two miles west of the Thompson-McKinney place, where it swings abruptly north for a mile or more, only to resume immediately its westward course, forming for some miles the northern boundary of the valley known as the " Boiling-Springs Prairie," beyond which it trends somewhat

Jan 1, 1890