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By I. E. Puddington

The property of surface tension in liquids is said to have been known to Leonardo de Vinci in about 1500. Approximately'300 years later Thomas Young and others provided the ground rules relating surface tension to the wetting of solids and to the pressure drop across curved surfaces. In retrospect it seems remarkable that more than 100 additonal years were required for substantial technological use to be made of the-information. Thus super critical and freeze drying to avoid shrinkage of finely divided solids have only seen industrial use since the 1930's and doubtless additional possible applications will be equally slow in finding concurrence of conditions to make them attractive economically. The use of a second liquid phase that preferentially wets ,a suspended solid as a flocculant for that solid was pointed out in 1943 (1). Combining this phenomenon with mechanical energy to alter the morphology of the flocs or with surface chemistry to utilize it in the selective flocculation in mixed solids required more than an additional decade. A major stimulant in advancing surface energy based technology 'of suspensions was the report by D. I. Stock in 1952 (2) that mechanical agitation of a dry suspension of barium sulphate in benzene produced dense microspheres of the solid with highly desirable sedimentation characteristics. Investigation of this observation revealed that it resulted from small quantities of water in the system and mechanistically the phenomenon was identical with that reported in 1943.withthe addition of mechanical packing (3). Here then was a base from which to separate more efficiently suspended solids, to make small spheres from powders, to separate selected components from mixtures of finely divided solids or to break emulsions. Each of these possible branches of technology has been slow in developing on other than an experimental scale although considerable

Jan 1, 1979

By D. G. Swarthout, J. W. Savage, R. W. Guard

The Nb-N constitution diagvam has been examined from 1100° to 1450°C at 1 atm N2 pressure. On the basis of- our work plus that of Brauer and coworkers the stable nitvide Phases are: a) a solid solutlion, basic niobium (bcc) with nitrogen contained interstitially; NbN,, x = <0.40; b) ß NhNx,x = 0.39 to 0.45; hexagonal (W2C type) (NbzN); a =3.058A,c = 4.961 + 0.001A c) y NbNx x = 0.75 to 0.80; tetragonal (distorted NaCl type) (Nb4N3); a = 4.386A,c = 4.332 + 0.001A; d) 6 NbN,, x = 0.88 to 0.91; cubic (NaCl type); a = 4.3885 + 0.0007A; e) E NbNx x = 0.92 to 1.00; hexagonal (Tip type); a = 2.958A, c = 11.272 * 0.0015A. In addition, a metastuble transition phase 6&apos; has been observed and occurs only during the transition 6 — E. 6&apos; NbN has these distinguishing parameters: NbNx,x = 0.96; hexagonal (anti-NiAs type); a = 2.94A, c = 5 .46A. The high-temperature phase fields in the system are governed by two reactions: a) 6 + Y + E, a entectoid reaction occurring at 1270" ± 20° C; b) o + N2 = E, a 2 012 1 reaction occurring at 1370" ± 20° C. As part of a study of the electronic low-temperature. properties of transition metal nitrides, a number of specimens of niobium nitride were prepared. Preliminary observations on these specimens showed several points of disagreement with data already in the literature. It was, therefore, decided to determine the constitution diagram for the Nb-N system between 1100" and 1450°C. The objective of this research was to define the temperature and composition regions of stability of the various phases and to explain the differences among previously proposed diagrams. Review of Previous Literature. The research on the Nb-N system to 1964 has been summarized by storms.&apos; Although he does not present a phase diagram, his review covers the research on the system thoroughly. One of the earliest works on NbN is that of Ascher-mann and coworkers2 who studied the superconductivity of the cubic 6 NbN. Subsequent work by Horn and ziegler,3 Cook, Zemansky, and Boorse,1 Rögener:5 Schroder6 and sellmaier7 has qualitatively confirmed the first results on superconductivity, although their methods of preparation differed considerably. The constitution diagrams proposed for the system by Brauer and Esselborn8 and Elliott9 are shown in Fig. l(a)and (b). The diagram in l(a) has been modified by more recent results in Brauer&apos;s laboratory (private communication). Although 6&apos; is shown on this diagram, Brauer has indicated that he now believes 6&apos; to be a metastable phase in the temperature range shown. The diagram of Elliott, Fig. l(b), is based primarily on the results of Elliott and Komjathy10 on ni-trided niobium strip or rod specimens examined by X-ray diffraction and metallography. It will be noted that these proposed diagrams are in conflict with respect to the temperature and composition ranges of

Jan 1, 1968

By Eugene F. Broome, Hugh A. Walls

A diffusion measurement technique based on a shear cell comprised of only two segments is described. The diffusion boundary value problem for the finite capillary geometry is solved in general for any arbitrary initial concentration profile and is subsequently specialized for the modified shear cell problem. Effects of convection and mixing at the shear interface were found to be negligible. Mercury self-diffusion coefficients were determined from -25° to 252°C. These data are in good agreement with those found by Meyer. ALTHOUGH diffusion in liquid metals has been of interest for over two centuries, the need for measurement techniques of improved accuracy and precision has become increasingly apparent as additional data have been obtained and theory has become more refined. These conditions reflect the experimental difficulties inherent in liquid diffusion measurements, in which transport by other processes, such as convection, tends to mask the diffusive transport. Frequently the disagreement between several theoretical predictions is less than that found between different sets of data obtained for a system. Moreover, as has been shown by Nachtrieb,1 diffusion data are needed over much larger temperature ranges if the functional dependence on temperature is to be known. Thus, improved techniques must be devised if experimental data are to augment fundamental understanding of the liquid state and to meet technological needs. The available techniques have been discussed elsewhere.&apos; Of these, only the capillary-reservoir, long capillary, and shear cell techniques will be discussed briefly in terms of experimental advantages and disadvantages. These methods served to establish design criteria for the modified shear cell described here. The capillary-reservoir technique of Anderson and saddington3 has been the most widely used method in recent years. The method offers experimental simplicity relative to other methods and has been employed for high-temperature measurements. Moreover, the mathematical relationship between the measured concentration ratio and the diffusion coefficient is such that smaller values of the ratio are achieved for a specified diffusion time relative to other methods. The amplified errors between the concentration ratio and the calculated diffusion coefficient are diminished at lower values of the ratio.&apos; The method also permits multiple determination by the simultaneous use of several capillaries. Disadvantages of the capillary-reservoir method are primarily associated with the hydrodynamic ef- fects of convection and of placing the capillary in the reservoir. These effects are most pronounced in the region near the open end of the capillary and produce an ill-defined boundary condition between the capillary and the reservoir. Such effects are not amenable to experimental or mathematical correction2 (although this has been suggested4). The long-capillary method of Careri, Paoletti, et al.5-10 involves filling one half of a small capillary tube of 150 to 200 mm total length with material of one composition or radioactivity and the other half with the second part of the diffusion couple. This arrangement eliminates the adverse hydrodynamic effects associated with the capillary-reservoir technique; however, certain other experimental difficulties are encountered in this method. The more significant of these difficulties involve the melting, expansion, contraction, and solidification of the diffusion system. The dependence in some cases of the diffusion coefficient on the capillary diameter noted by Careri et a1.7 (termed the "wall effect") has been alternatively explained by Nachtriebl as a convection effect during solidification. In mutual diffusion measurements, the convection problems associated with melting and solidification are increased because of the differences in melting points and in expansion coefficients between the halves of the diffusion couple. However, the errors caused by convection effects within this method are usually less than those in the capillary-reservoir method. Furthermore, the concentration profile needed to determine concentration-dependent diffusion coefficients by the Boltzmann-Matano analysis can be obtained from this method. Of the previous attempts to use shear cells, only the cell used by Nachtrieb and Petit11,12 appears to have yielded good data. They reduced the mechanical complexity of the conventional shear cell by using a cell comprised of only four segments. Three of these segments were filled with ordinary mercury and the fourth with radioisotopic mercury in their determination of mercury self-diffusion coefficients. The average concentration (radioactivity) was determined in each segment following a period of isothermal diffusion. These concentration values were fitted to concentration profiles obtained from the Stefan-Kawalki tables, and the diffusion coefficients were evaluated. Thus, although the number of cell segments is reduced in their method, some information about the concentration profile can be obtained in terms of the Stefan-Kawalki analysis. Moreover, their cell is suitable for measurement of diffusion coefficients at elevated pressure, as they successfully demonstrated with mercury. Consideration of the design and experimental features of the methods discussed above suggested several criteria for the new cell: 1) a &apos;&apos;total" capillary system, as opposed to a capillary-reservoir system, should reduce adverse convection effects; 2) such a capillary system should avoid the problems en-

Jan 1, 1969

By H. W. Page

Petroleum requirements since V-J day have been appreciably higher than predicted. Foreign operations now exceed maximum wartime levels by about 14 per cent. Domestic operations since V-J day have averaged 92 Per cent of the wartime peak. In spite of maximum foreign refinery runs, large exports of all products, except residual fuel oil, are necessary to meet foreign demand. During the next few years it is expected that foreign operations will continue at capacity, including new installations, but that, because of increases in foreign demand, exports will continue at about their present level. Domestic operations will increase during this period and crude production probably will exceed maximum efficient rates. Even after 10 years some exports probably will be required, but eventually these will be supplanted by increased output of foreign refineries, except for small tributary exports. The increase in domestic requirements will exceed the decline in exports. Unless findings of crude oil exceed present expectations, the increasing demand will be met by increased imports and synthetic methods-—such as the Hydrocarbon Synthesis Process for conversion of natural gas and coal to gasoline and distillates. Catalytic cracking installations will increase as crude availability decreases. This will help to meet the increasing demand for gasoline but will intensify the domestic shortage of residual fuel oil. Eventually larger imports will be required to satisfy the demand for this product. Introduction Under the pressure of the wartime period, there was time only occasionaly to look ahead in anticipation of what the postwar era held for the petroleum industry. Perhaps the general expectation was that a rather pronounced decline in the level of industry petroleum operations would take place shortly after the end of the war, with the impact felt mainly on the economy of the United States- It is of interest now, nine months after V-J day, to take inventory of the near-term situation and see what significant forces are at work. With this as a starting point, it should be possible to engage in something more satisfactory than pure speculation concerning trends in the immediate future and 10 to 20 years ahead. Present and Near-term Situation During the nine-month period following V-J day, foreign crude oil production and rebery operations have actually increased the These activities were at maximum capacity on V-J day but the continuation of drilling programs, the completion of new and rehabilitated refineries and of transportation facilities during the Past nine months have increased the foreign capacity. This added capacity has been fully utilized. Foreign crude oil production in May 1946 is about 14 per cent higher than during July 1945 and refining operations some 12 per cent higher&apos; During the same period there has been a falling off in similar activities within the

Jan 1, 1947

By N. J. Grant, B. C. Giessen, M. Morris

The slvuclures of alloys in the system In-Bi have been investigated after (levy vapid queuching from the mell (splat cooling) to -190°C. Tuo-phase fields could be suppressed over most of the tota1 concentvalion range; five melastable phases a1, a2, ?, ?1. and ß exisl, of which four have simple elementtike structures. For example, ß has the A5 struclure of white till. Crystal-tographic data and coordination numbers for these phases aye given, as well as addilional information on the equilibrium diagram, where a new phase In5Bi3 teas found. THE phase diagrams of binary combinations of B elements from the groups B2, B3, B4, and B5 are usually of a simple type and show considerably fewer intermediate phases than combinations of these elements with A metals, transition metals, or the B1 noble metals. Aside from phases such as the typical B3-B5 compounds with the ZnS-B3 structure type, few stoichiometric phases are known; among them are In2Bi and 1nBi.l Nonstoichiometric phases include ß (In-Sn), a1, (In-Pb), and the tin-rich ? phases in the In-Sn, Cd-Sn, and Hg-Sn systems.&apos; The first two phases have a close relationship to indium, while the latter group are known to be structurally related to a Sn. Thus, there are generally no immediate experimental data for the correlation of the crystal structures of B metals and B metal combinations with certain monotonously varying parameters, such as the valence electron concentration (VEC), or the average atomic size. Such parameters have been recognized as structure determining, e.g., for the transition 4 Sn — y phase,2,3 where nonintegral valence electron concentrations are encountered. It should be possible to extend such correlations to other binary systems, if nonequilibrium single-phase alloys could be produced over broad valence electron concentration ranges, and if their crystal structures could be regarded as being imposed by their electronic states. It has been shown in the case of the tin-rich 7 phases3 that alloy phases with typical crystal structures can be produced in B metal alloys rapidly quenched from the liquid to -190°C by the splat cooling technique due to Duwez,3-8 and reviewed in Refs. 5 and 6. The In-Bi system was selected because it extends over a valence electron concentration range in which several metastable, nonstoichiometrir phases could be expected to occur. Further, the low melting points of the known intermediate phases, In2Bi and InBi, Fig. 1(a), indicated low binding energies and thus possibly low driving forces for the formation Of the equilibrium structures. EXPERIMENTAL TECHNIQUES AND RESULTS The preparation of the quenched foils followed the practice described in Ref. 3. Master alloys were produced by melting of indium (99.97+) and bismuth (99.99+) in evacuated Vycor capsules or in an inert gas arc furnace; quantities of 20 mg were splat-cooled onto copper and silver substrates held at - 190°C; and crystal structures and lattice parameters were determined on a GE XRD-5 diffractometer using Cu Ka, radiation at -190°C and at room temperature. The duplication of each run with both substrates permitted the elimination of overlap of the substrate diffraction pattern and that of the investigated substance. The XRD patterns were usually taken from sin2 " = 0.03 to 0.35; the substrate was used as a means of internal calibration. The fractional accuracy of the lattice parameters of metastable phases is approximately 10-3 In the following, all percentages are in atomic percent. The stable and metastable phases found after rapid quenching to -190°C are listed in Table I, together with estimated concentration ranges and crystallographic data. The investigated alloys and phases present in them are given in Table 11. Except for the region between indium with 33 and 50 pct Bi, where a revision of the equilibrium phase diagram became necessary to include a new stoichiometric phase In5Bi3, the diffraction patterns taken after heating to room temperature agreed with those expected from the phase diagram, Fig. l(a). This suggests that the new nonstoichiometric phases are not stable at room temperature, thus following the observations made for the y phases based on tin.3 Results concerning the equilibrium phases In2Bi and In5Bi3 and the revision of the equilibrium phase diagram which is made necessary by the inclusion of In5Bi3 will be treated first. The Crystal Structure of In2Bi. Makarov7 had identified In2Bi as belonging to the AlB2-C32 type ; however, in a later paper the structure was revised.8 In2Bio was found to be of the Ni21n-B8ß type,21 with a = 5.496A, c = 6.57.9A, and N = 6 atoms per unit cell.9 This crystal structure was confirmed in the present work; definite evidence for the doubling of the c axis, as compared to the A1B2-C32 type, and for the proposed order structure, was found in the powder pattern. The observed lattice parameters agree well with those of Ref. 8; those measured at -190°C are given- in Table I. The Crystal Structure of In5Bi3. A new, equilibrium, intermediate phase was identified in slow-cooled, as-cast alloys; it was identified as In5Bi3. The structure has been worked out by Giessen and Grant;" lattice parameters at -190°C are given in Table I. This phase is probably identical with "In3Bi2", produced by vapor deposition techniques, but not recognized as an equilibrium phase by Palatnik et a1.11 After completion of the present work, the existence of In5Bi3 has also been demonstrated by superconductivity measurements on In-Bi alloys.20

Jan 1, 1968

By H. W. Page

Petroleum requirements since V-J day have been appreciably higher than predicted. Foreign operations now exceed maximum wartime levels by about 14 per cent. Domestic operations since V-J day have averaged 92 Per cent of the wartime peak. In spite of maximum foreign refinery runs, large exports of all products, except residual fuel oil, are necessary to meet foreign demand. During the next few years it is expected that foreign operations will continue at capacity, including new installations, but that, because of increases in foreign demand, exports will continue at about their present level. Domestic operations will increase during this period and crude production probably will exceed maximum efficient rates. Even after 10 years some exports probably will be required, but eventually these will be supplanted by increased output of foreign refineries, except for small tributary exports. The increase in domestic requirements will exceed the decline in exports. Unless findings of crude oil exceed present expectations, the increasing demand will be met by increased imports and synthetic methods-—such as the Hydrocarbon Synthesis Process for conversion of natural gas and coal to gasoline and distillates. Catalytic cracking installations will increase as crude availability decreases. This will help to meet the increasing demand for gasoline but will intensify the domestic shortage of residual fuel oil. Eventually larger imports will be required to satisfy the demand for this product. Introduction Under the pressure of the wartime period, there was time only occasionaly to look ahead in anticipation of what the postwar era held for the petroleum industry. Perhaps the general expectation was that a rather pronounced decline in the level of industry petroleum operations would take place shortly after the end of the war, with the impact felt mainly on the economy of the United States- It is of interest now, nine months after V-J day, to take inventory of the near-term situation and see what significant forces are at work. With this as a starting point, it should be possible to engage in something more satisfactory than pure speculation concerning trends in the immediate future and 10 to 20 years ahead. Present and Near-term Situation During the nine-month period following V-J day, foreign crude oil production and rebery operations have actually increased the These activities were at maximum capacity on V-J day but the continuation of drilling programs, the completion of new and rehabilitated refineries and of transportation facilities during the Past nine months have increased the foreign capacity. This added capacity has been fully utilized. Foreign crude oil production in May 1946 is about 14 per cent higher than during July 1945 and refining operations some 12 per cent higher&apos; During the same period there has been a falling off in similar activities within the

Jan 1, 1947

By W. W. Smeltzer

The linear formation rates of wustite films have been determined over the temperature range 590° to 1030°C using a vacuum microbalance technique. These rates are dependent directly on the partial pressure of carbon dioxide, Activation energies for film and scale formation in carbon dioxide and oxygen atmospheres are equivalent to either the dissociation energies of carbon dioxide and oxygen, or the activation energy for the diffusion of cation vacancies in wustite. Of the metals, iron is the most widely used basic constituent of durable alloys despite its intrinsic property of converting at a relatively rapid rate to the oxides from which it is derived. This property has accounted partially for many investigations on the oxidation of iron at low and high temperatures. Interpretation of the results have been complicated by formation of multilayers containing the various oxide phases. To aid in elucidation of the oxidation kinetics, measurements have been carried out in this investigation on the growth of the wustite surface layer. There are several studies directly related to the objective of this investigation. The growth of multilayer scales has been demonstrated to be diffusion controlled in oxygen at atmospheric pressure over the temperature range 450" to 1200°C by Davies, Simnad, and Birchenall.&apos; To gain an insight into the diffusion mechanism, Himmel, Mehl, and ~irchenall&apos; determined the self-diffusion coefficients of iron in wustite, magnetite, and hematite. These results were used to evaluate the oxidation rates of iron and its oxides, taking as a basis the theoretical parabolic rate equation developed by Wagner., The evaluations were compared to experimental data and were shown to provide essential confirmation of this theory. Fischbeck, Neundeubel, and salzer4 have demonstrated that the oxidation of iron in carbon dioxide and other atmospheres at high temperature obeys a linear relationship. Because the Arrhenius temperature coefficients of the reaction rate constants changed at the A, point they concluded that the passage of iron into the oxide controlled the reaction. This viewpoint has been accepted by Benard and ~albot&apos; to explain the occurrence of linear rates in oxygen before the onset of diffusion-controlled parabolic oxidation. This basic premise of a rate-controlling reaction at the iron/oxide interface has been questioned recently by Hauffe and Pfeiffer.&apos; Since the formation of wustite may follow a linear or parabolic relationship depending on the pressure of the gaseous re-actant, they propose that linear oxidation is determined by a chemisorption reaction while parabolic oxidation is controlled by diffusion. As confirmation of this viewpoint, Hauffe and pfeiffer6 and Pfeiffer and ~aubmeyer&apos; have established that the linear scaling constants of wustite formation at 1000°C in carbon-dioxide or low-pressure oxygen atmospheres

Jan 1, 1961

By Floyd C. Kelly

A. HUltgren, .Söderfors, Sweden (written discussion*).—From the results obtained in his own experiments as well as those of Austin and of Grube Mr. Kelley derives a general law, expressed tentatively in the following words: "whenever two metals are brought into intimate contact at a temperature at which diffusion takes place, a comparatively rapid, or abnormal, grain growth results." It is suggested that,, in order adequately to represent the facts, this definition should he restricted by the following qualifications: a and b are the two metals, b diffusing into a. A. At the temperature in question a should exist as phase a 1 having a limited solubility for b. B. The supply of b by diffusion should be sufficient, in view of the rate of diffusion into a 1, to increase the concentration of b above the saturation value in a 1 so as to cause a new phase a2 to form. (7. The phase a2 should have a range of solubility for 6, thus rendering continued diffusion possible. D. In order that the columnar grains may be preserved in the structure the phase a2 should, of course, not suffer transformation on cooling. The phenomenon thus defined may be described as progressive transformation by diffusion. Its mechanism would appear to he as follows: Fig. 17 shows a portion of the equilibrium diagram a-b, Fig. 18 the distribution of b in solution after various periods of diffusion, Fig. 19 represents the structure in cross-section of a cylindrical rod of a at the end of heating period 3. 1. The first effect of diffusion of b into a will be to establish a concentration gradient in phase a1 (1, Fig. 18). When the saturation value for the temperature of the experiment (m, Fig. 17) is reached at the surface, nuclei of, a2 of composition n will form here, and later develop into a continuous layer. Assuming that diffusion proceeds without irregularities and that transformation at any point sets in without lag—i. e., in the moment saturation is exceeded—the transformation a1-a2 will advance inwards on a cylindrical surface concentric with the surface of the rod. The discontinuity of composition at the transformation surface in the position it happens to have at the end of the treatment (3, Fig. 18) will be preserved at room temperature, if the cooling is not particularly slow, and be recorded in the structure as a marked, smooth line, in agreement with Grube&apos;s and the author&apos;s observations. The shape of the distribution curves in Fig. 18 is also corroborated by the analyses given by Grube. 2. During diffusion, since the secondary phase a2 is always in immediate contact with the saturated part of the primary phase a1, there should be very little lag in the transformation. This means that the first a2 grains formed should grow in preference to the formation of independent nuclei; in other words, columnar growth results. It does not seem necessary to assume, with Green,&apos; whose conception of the phenomenon

Jan 1, 1929

By Floyd C. Kelly

A. HUltgren, .Söderfors, Sweden (written discussion*).—From the results obtained in his own experiments as well as those of Austin and of Grube Mr. Kelley derives a general law, expressed tentatively in the following words: "whenever two metals are brought into intimate contact at a temperature at which diffusion takes place, a comparatively rapid, or abnormal, grain growth results." It is suggested that,, in order adequately to represent the facts, this definition should he restricted by the following qualifications: a and b are the two metals, b diffusing into a. A. At the temperature in question a should exist as phase a 1 having a limited solubility for b. B. The supply of b by diffusion should be sufficient, in view of the rate of diffusion into a 1, to increase the concentration of b above the saturation value in a 1 so as to cause a new phase a2 to form. (7. The phase a2 should have a range of solubility for 6, thus rendering continued diffusion possible. D. In order that the columnar grains may be preserved in the structure the phase a2 should, of course, not suffer transformation on cooling. The phenomenon thus defined may be described as progressive transformation by diffusion. Its mechanism would appear to he as follows: Fig. 17 shows a portion of the equilibrium diagram a-b, Fig. 18 the distribution of b in solution after various periods of diffusion, Fig. 19 represents the structure in cross-section of a cylindrical rod of a at the end of heating period 3. 1. The first effect of diffusion of b into a will be to establish a concentration gradient in phase a1 (1, Fig. 18). When the saturation value for the temperature of the experiment (m, Fig. 17) is reached at the surface, nuclei of, a2 of composition n will form here, and later develop into a continuous layer. Assuming that diffusion proceeds without irregularities and that transformation at any point sets in without lag—i. e., in the moment saturation is exceeded—the transformation a1-a2 will advance inwards on a cylindrical surface concentric with the surface of the rod. The discontinuity of composition at the transformation surface in the position it happens to have at the end of the treatment (3, Fig. 18) will be preserved at room temperature, if the cooling is not particularly slow, and be recorded in the structure as a marked, smooth line, in agreement with Grube&apos;s and the author&apos;s observations. The shape of the distribution curves in Fig. 18 is also corroborated by the analyses given by Grube. 2. During diffusion, since the secondary phase a2 is always in immediate contact with the saturated part of the primary phase a1, there should be very little lag in the transformation. This means that the first a2 grains formed should grow in preference to the formation of independent nuclei; in other words, columnar growth results. It does not seem necessary to assume, with Green,&apos; whose conception of the phenomenon

Jan 1, 1929

By A. J. Williams

THE province of Saskatchewan, situated in the center of the Great Plains region of Canada, has, like most prairie areas, an essentially agricultural economy. Most of its population of about 860,000 is located in the southern half of the province in the farming and ranching areas. To the north of the prairie is a broad forested belt supporting a considerable timbering industry, and the northern one third of the province is glaciated pre-Cambrian rock formation. This latter area is relatively barren of vegetation, but the presence within it of a considerable variety of radioactive, noble and base metals, and industrial minerals has been shown by prospecting in recent years.&apos; Glacial Geology The Keewatin ice sheet, considered to have accumulated in the country to the west of Hudson Bay in Pleistocene time, covered at its maximum advancement almost all of Saskatchewan and extended south of the international boundary. Only in the Cypress Hills in the southwest and around Wood Mountain in the south central portion of the province did the preglacial formations escape the action for this glacial period. The bedrock of the plains and forest areas therefore is overlain by moraines and modified glacial drift, which vary in thickness from a few feet to 400 or 500 ft.&apos; Glacial action in the pre-Cambrian area of the province was largely erosional, most of the more recent formations and some of the pre-Cambrian rock being transported out of the area to the south and west. It has been estimated that about 13 pct of this area is composed of lakes and rivers not too adaptable to rail or water transportation, so that until the use of aviation for exploration purposes became general, development of the area was slow. To the south, the heavy mantle of glacial drift has to some extent deterred the discovery of industrial minerals in the bedrock underlying the forest and prairie regions3 At the same time, this drift contains numerous deposits of those most elementary and necessary industrial minerals, sand and gravel. Sedimentary Basin The major feature of the sedimentary deposits underlying the plains regions is the basinal structure known as the Moose Jaw syncline, which runs from the southeast corner of the province in a northwesterly direction. To the west of this syncline the formations curve upward, then have been faulted and further upthrust to appear at the surface in the foothills of the Rockies in Alberta; to the east and north they curve upward into Manitoba and northern Saskatchewan, but the surface contacts are covered mostly with glacial drift.238 The axis of the syncline dips to the southeast, so that there is also an upward trend of the formations along the axis to the northwest. In illustration of the regional structure underlying the province, the pre-Cambrian basement has been logged in drillholes at the following depths in several locations: Ogema (south central), 9390 ft; Gronlid (northeast), 2599 ft; Vera (northwest), 4422 ft; Big River (north northwest), 2348 ft. Fig. 1 indicates the general surface geology of the province, ignoring such glacial overburden as may overlie many of the bedrock formations. Also indicated is the approximate location of the axis of the Moose Jaw syncline.&apos; Industrial Minerals Clays: The province is fortunate in possessing a widespread distribution of clays of ceramic value, ranging from those used for heavy structural products to the high grade pottery and china clays. Shales suitable for brick and tile production are found in the Upper Cretaceous and Tertiary formations across the south of the province where the glacial drift is thin or nonexistent. Many deposits of glacial lake clays suitable for such wares are found scattered over the rest of the province south of the pre-Cambrian area. The Whitemud formation of the Upper Cretaceous is a narrow sedimentary band of secondary clays found intermittently at points across the south of the province where glacial action did not disturb or remove them.&apos; In the southwest corner of the province, around Eastend in the Frenchman River valley, the refractory clays of this formation are contaminated somewhat with iron compounds or other alteration products of basaltic rocks. This eliminates the use of those clays in true whitewares, as they fire to creamy buff shades at the lower temperatures and to a blue-specked grey at cone 8 to 12, (2280°F to 2390°F), the range commonly used in firing whiteware. However, for use in the production of colored artware, caneware, stoneware or crockery, and sewerpipe, this type of clay makes an excellent body that requires little or no addition of flint, feldspar, or other fluxing materials such as are required in the higher class of ware.&apos; It is not a grade of clay that can be shipped great distances to the manufacturing centers, but a market for considerable tonnages has developed at nearby Medicine Hat, where cheap natural gas is available for the firing of the ware. Farther east in the south central portion of the province, the clays of the Whitemud formation are generally more refractory and white burning. The formation is divided into three zones, consisting of white clays, brown shale, and white sandy clays.

Jan 1, 1953

By G. B. Gibbs

Equations are developed which describe the growth of graphite nodules during a-phase graphi-tization under various limiting conditions. When carbon diffusion is rate controlling a modified Birchenall-Mead equation predicts an "apparent activation energy" of 31 keal mole-1 for the parabolic growth constant. If reaction at the graphite or cementite interface is the slowest process growth kinetics are linear and the activation energy must be >50 keal mole-1. A comparison with the experimental observations confirms that carbon diffusion determines the rate of reaction. Apart from minor approximations associated with Lou! carbon solubility in a iron the theory may also be applied to I-phase graphitization. It is well-known that cementite exists as a meta-stable phase in Fe-C alloys and that if a specimen is held at diffusion temperatures for a sufficiently long period the cementite decomposes and graphite is precipitated. Graphitization occurs by the nu-cleation and growth of carbon nodules and several impurity elements catalyze the reaction when present in minute amounts.1 The growth kinetics of nodules have been extensively investigated in the fee ? range2, 3 and recently in the bee a range.1, 4 Experimental growth curves (nodule radius vs time) have slopes which decrease with time, but the scatter of points is generally too great for the precise shape of the curves to be determined with certainty. Birchenall and Mead5 concluded that they are parabolic in ? iron, indicating diffusion control, and that the migration of carbon atoms determines the growth rate. Harris et al, 1 advanced similar ideas for a-phase graphitization. On the other hand, Burke3 chose to regard the initial growth region as a transient followed by a linear law indicating interface control (i.e., cementite decomposition or graphite crystallization as the slowest process). Jeminson and Higgins6 originally considered the initial steep portions of "parabolie" to represent a linear growth law also. In support of these ideas it has been noted that the apparent ac-

Jan 1, 1965

By W. T. Bishop

For many years pine oil has been used extensively as a frother for the flotation of minerals, particularly sulphides, yet the published information available to the average user on its composition, chemical and physical properties, has been rather meager. It is the purpose of this paper to discuss these points and their relationship to the frothing properties of pine oil used in flotation processes. Pine oil, as the name implies, is a liquid obtained from the processing of wood of the longleaf and other southern pines. It is a complex mixture of naturally occurring terpene derivatives, primarily alcohols, and a smaller amount of terpenes, which has found many uses in various industries. Its use as a frother in flotation processes was the first large-scale application in industry and today the mining industry still consumes large quantities of pine oil but the textile and disinfectant industries consume comparable volumes. Much is used in soap manufacture and laundry operations. The surface-active properties of pine oil are in a large degree responsible for this versatility. History The name "Naval Stores" goes back to the days when pine tar and pitch were used to caulk leaky ships and &apos;Oat their ropes and rigging. Today this term is still used to include not only the oleoresinous products of the pine tree—rosin and turpentine— but other products such as pine oil, pine tar, and the many terpene and resinous compounds obtained by extracting the pine wood or tapping the tree. That part of the industry known as "wood naval stores" dates from about the beginning of this century and today produces a large part of the country&apos;s rosin and turpentine by processing pine wood. In addition, all of our natural pine oil is supplied by the wood naval stores industry, as tapping of the live tree gives only rosin and turpentine. This latter phase is known as the "gum naval stores " industry. The first successful commercial operation of the steam and solvent process of the wood naval stores in industry was carried out by Yaryan at Cadillac, Mich., in 1909.1 This operation did not prove profitable, so Yaryan went south to utilize the longleaf pine, and built a plant at Gulfport, Miss.2 Soon after, another plant was built at Brunswick, Ga., which is still in operation, and in 1914 was reported to have processed about 500 tons of wood per day.&apos; In 1921 Hercules Powder Co. acquired the Yaryan interests, at which time the production of pine oil was only 3 to 5 million pounds per year and flotation was the largest customer. As time went on, technological advances were made, other companies entered the field, and the production of pine oil increased many fold. The growth of the industry was especially marked during the past 10 years, and in

Jan 1, 1947

By W. T. Bishop

For many years pine oil has been used extensively as a frother for the flotation of minerals, particularly sulphides, yet the published information available to the average user on its composition, chemical and physical properties, has been rather meager. It is the purpose of this paper to discuss these points and their relationship to the frothing properties of pine oil used in flotation processes. Pine oil, as the name implies, is a liquid obtained from the processing of wood of the longleaf and other southern pines. It is a complex mixture of naturally occurring terpene derivatives, primarily alcohols, and a smaller amount of terpenes, which has found many uses in various industries. Its use as a frother in flotation processes was the first large-scale application in industry and today the mining industry still consumes large quantities of pine oil but the textile and disinfectant industries consume comparable volumes. Much is used in soap manufacture and laundry operations. The surface-active properties of pine oil are in a large degree responsible for this versatility. History The name "Naval Stores" goes back to the days when pine tar and pitch were used to caulk leaky ships and &apos;Oat their ropes and rigging. Today this term is still used to include not only the oleoresinous products of the pine tree—rosin and turpentine— but other products such as pine oil, pine tar, and the many terpene and resinous compounds obtained by extracting the pine wood or tapping the tree. That part of the industry known as "wood naval stores" dates from about the beginning of this century and today produces a large part of the country&apos;s rosin and turpentine by processing pine wood. In addition, all of our natural pine oil is supplied by the wood naval stores industry, as tapping of the live tree gives only rosin and turpentine. This latter phase is known as the "gum naval stores " industry. The first successful commercial operation of the steam and solvent process of the wood naval stores in industry was carried out by Yaryan at Cadillac, Mich., in 1909.1 This operation did not prove profitable, so Yaryan went south to utilize the longleaf pine, and built a plant at Gulfport, Miss.2 Soon after, another plant was built at Brunswick, Ga., which is still in operation, and in 1914 was reported to have processed about 500 tons of wood per day.&apos; In 1921 Hercules Powder Co. acquired the Yaryan interests, at which time the production of pine oil was only 3 to 5 million pounds per year and flotation was the largest customer. As time went on, technological advances were made, other companies entered the field, and the production of pine oil increased many fold. The growth of the industry was especially marked during the past 10 years, and in

Jan 1, 1947

By E. H. Rose

The present symposium on flotation machines provides a unique opportunity for group reappraisal of standard or habitual viewpoints. A symposium is by definition a trading post- for observations that might prove complementary when put together, thus leading to useful thoughts that might not have been evident from the original observations individually. The present paper, pertaining to power consumption in flotation, is deliberately an experiment of that kind. Data were solicited from the operating superintendents of several of the major flotation plants on this continent. The information received, covering a total of 14 separate operations in seven plants, has been collated in terms of power intensity; that is, the total power input per cubic foot of cell volume. This departs somewhat from the conventional expression of power per ton of ore treated, though the latter figure is also given for the plants concerned. Because of wartime restrictions, particularly in Canada, identifying names of plants and machines are withheld. Not as a firm conclusion, but as a tender for symposium discussion, the following points are made: 1. That flotation is a power operation in much the same sense as ball milling. 2. That contact time is the complement of power intensity and may be decreased as the latter is increased. 3. That a decrease in flotation power per ton of ore can result from an increase in power intensity. Analogy with Grinding In grinding, it has become axiomatic that the more the power put into a given operation, the greater the work performance. The analogous view is now proposed that the effectiveness of any flotation operation will be related to the mechanical energy usefully applied to that operation. Under this view, each increment of properly directed input energy should give either an increase in unit tonnage or an improvement in the metallurgical separation (concentrate grade or tailing grade), until either the theoretical limit imposed by mineral constitution or surface condition is reached, or until further increments of power become uneconomic under the law of diminishing returns. Thus, as in grinding, there are two forms of output that greater power input or improved utilization of power can produce. As for the law of diminishing returns, lower unit cost of power through improved generating efficiency in the past decade has pushed the limit back. Over and above this, however, there is strong indication in the operationg data herein presented that higher power intensity results in an actual economy of over-all power consumption. Like crushing and grinding, flotation accomplishes a rupture of the forces of molecular attraction, by taking particles from the common environment and placing them in the two separate environments of

Jan 1, 1947

By E. H. Rose

The present symposium on flotation machines provides a unique opportunity for group reappraisal of standard or habitual viewpoints. A symposium is by definition a trading post- for observations that might prove complementary when put together, thus leading to useful thoughts that might not have been evident from the original observations individually. The present paper, pertaining to power consumption in flotation, is deliberately an experiment of that kind. Data were solicited from the operating superintendents of several of the major flotation plants on this continent. The information received, covering a total of 14 separate operations in seven plants, has been collated in terms of power intensity; that is, the total power input per cubic foot of cell volume. This departs somewhat from the conventional expression of power per ton of ore treated, though the latter figure is also given for the plants concerned. Because of wartime restrictions, particularly in Canada, identifying names of plants and machines are withheld. Not as a firm conclusion, but as a tender for symposium discussion, the following points are made: 1. That flotation is a power operation in much the same sense as ball milling. 2. That contact time is the complement of power intensity and may be decreased as the latter is increased. 3. That a decrease in flotation power per ton of ore can result from an increase in power intensity. Analogy with Grinding In grinding, it has become axiomatic that the more the power put into a given operation, the greater the work performance. The analogous view is now proposed that the effectiveness of any flotation operation will be related to the mechanical energy usefully applied to that operation. Under this view, each increment of properly directed input energy should give either an increase in unit tonnage or an improvement in the metallurgical separation (concentrate grade or tailing grade), until either the theoretical limit imposed by mineral constitution or surface condition is reached, or until further increments of power become uneconomic under the law of diminishing returns. Thus, as in grinding, there are two forms of output that greater power input or improved utilization of power can produce. As for the law of diminishing returns, lower unit cost of power through improved generating efficiency in the past decade has pushed the limit back. Over and above this, however, there is strong indication in the operationg data herein presented that higher power intensity results in an actual economy of over-all power consumption. Like crushing and grinding, flotation accomplishes a rupture of the forces of molecular attraction, by taking particles from the common environment and placing them in the two separate environments of

Jan 1, 1947

By Sidney Swensrud

ABOUT a year ago, I attempted in a general way to trace the origin and development of some of the marketing problems of the petroleum industry, and to describe certain trends which it then seemed possible to foresee. To summarize briefly, it was pointed out that the consumption of gasoline, after increasing for more than a decade at an almost unbelievable rate, was slowing down, but that the two factors which determined the supply of gasoline-namely, the production of crude oil and the percentage of gasoline derived therefrom-were tending steadily to mount. It was suggested that, while the increase in gasoline outlets began with and probably was justified at the start by the rapidly increasing demand, long after all reasonable requirements as to number of outlets had been met the number continued to increase-if anything, at a still more rapid rate-because by that time the overproduction of crude had begun to exert an impelling urge upon the owners of that crude to seek assured outlets for it in the form of gasoline. As more and more companies became integrated all the way from crude oil to marketing, there took place an ever-increasing competition among them, not only for the existing outlets but for new ones. The wide margin between wholesale cost and retail price, which is characteristic of the early stages of most new industries, persisted in the oil industry longer. than in most industries, for various reasons. The existence of that wide margin provided in large measure the means of attracting new outlets, for as the gallonage per outlet declined with the increasing number of outlets, competing companies simply offered the dealers a larger part of the total margin. The very nature of competition suggests that such a process would continue until practically all of the available margin was thus given away, and such was clearly the, tendency. It was a system that in turn produced increasing marketing expense per gallon on account of the -diluted gallonage per outlet; this increased expense might seem to have provided a justification for continuing wide margins. Economics, like its parent, nature, however, progresses by mutations and so began to throw out new types of marketers, in the form cf tank-car service stations, cut-price jobbers, and the like-heretics or

Jan 1, 1932

By W. H. Emmons

The exploration of deposits of the metals will never become an exact science. There will always be an element of uncertainty in prospecting and developing mines. In countries where the surface has been closely scrutinized, most of the deposits whose outcrops contain valuable metals have probably been discovered. Many metalliferous deposits, however, are normally so much altered at the surface that the true significance of their outcrops is likely to be obscured. If a deposit is not exposed, its presence may become known by some one of its characteristics that is different in kind or in degree from a similar feature of the associated rock. Thus, a deposit that is not exposed may be discovered because of its magnetic property. So few minerals are strongly magnetic that the value of magnetic surveys is limited, but the dip needle has nevertheless proved of great aid in locating magnetic belts, and these in some regions are associated with workable iron ores. The Cuyuna Iron Range of Minnesota, which does not exhibit any outcrop of iron ore, was discovered by drilling "areas of attraction" that are due to belts of magnetic rocks associated with the iron ores. In some regions the use of the dip needle is justified, even if it does no more than reveal the strike of the rocks, since a knowledge of the latter enables the driller to locate and point his holes to advantage. The measures of gravity by the use of the pendulum are so accurate, or the limit of error is so small, that one might detect the presence of a concealed tabular deposit approximately at the surface, 34 ft. (10.36 m.) thick, having a density double that of the surrounding rocks. However, not many deposits have a density twice that of ordinary rocks and a thickness as great as 34 ft.; if they lie a short distance below the surface the density or the thickness must be even greater. Consequently, there is not much hope of sufficiently developing the gravity method of detecting deposits of heavy ores to make it of practical value. If the limit of error could be reduced to about one-tenth the present factor, and if the rather tedious and painstaking methods of determining gravity that are now in use could be simplified, the method would promise some degree

Jan 1, 1918

By John F. Blandy

With the Report of Mining Statistics, for the year 1872, there was published a geological map of the United States and Territories. This is, I believe, the only map which represents the geology of Arizona, and is, as far as my observations go, correct. It is, however, on so small a scale as to be of little practical value to the miner. I know of no other maps, even of localities, of this Territory. The topographical maps are also on so small a scale as not even to serve as guides from place to place; the largest, that of Eckhoff and Ricker, being only 30 by 30 inches to represent a territory of 135,000 square miles. For these reasons, it makes it exceedingly difficult to describe the various mining centres in an intelligent manner, and equally so to examine such a hilly country as it is intended to describe in this paper. When I first came into this Territory I soon realized the troubles I had to encounter in trying to form an opinion, or even to get the needed information on the geological contour. I have, therefore, labored as best I could to get a topographical diagram of the section of country represented by the map which accompanies this paper.* The lines run by the Land Department up the valleys of the Aqua Frio, and those west of the Hassayampa, and connected east and west to the north of Prescott, enabled me to inclose correctly the space covered by the Bradshaw and Sierra Prieta mountain groups, but the territory covered by these mountains, and the most difficult part, I have had to fill up as best I could. I have met with such success as to meet the approbation of those most familiar with the country, and, with the map in hand, any one would he able to cross it in any direction. As there has not been a single line of survey made across it, this has been no small undertaking, and I have had to depend upon sights from prominent points with the pocket-compass, or, in the absence of that, to make observations, with watch in hand, and guess as near as possible the meridian direction. Rut one main wagon-road passes through the district, that from Prescott to the Peck mine.

Jan 1, 1883

By A. Szirmae, Hsun Hu

The early stages of recrystallization in a 70 pct cold-rolled Si-Fe crystal of the (110) (0011) orientation were studied with a Siemens electron microscope. Orientation studies based on electron-diffractzotz. patterns confirm the results of previous texture analysis. The driving energy for recrystallizatior and the critical radius for growth were calculated from the dislocation energy and the energy of the subgrain bourzdaries, and it was found consistent with the observed size of the recrystallized grains. The recrystallization characteristics of crystals with different initial orientations are discussed. The recrystallization of cold-rolled (110)[001] crystals of Si-Fe has been widely studied by various investigators.1-4 Their results on both deformation and annealing textures are in good agreement. The rolling texture after 70 pct reduction consists mainly of two crystallographically equivalent (111) [112] type textures and a minor component of the (100) [011] type. The latter is derived from the deformation twins, or Neumann bands, which are formed during the early stages of deformation and later rotate to the (100) [011] orientation upon further rolling reduction. Between the two main (111) [112] type textures, there is some orientation spread, because of which very low intensity areas appear in the pole figure. If these very low intensity areas are considered to be a very weak component in the texture, then a (110) [ 001 ] orientation may be assigned to them. When this rolled crystal is annealed at a sufficiently high temperature for recrystallization, the texture returns to a simple (110) [001]. The purpose of the present investigation was primarily to seek a better understanding of the recrystallization process by using the electron transmission technique. The (110) [0011 type of crystal was selected because orientation data for it are well known from previous studies with conventional techniques. Direct observations on the recrystallization of such a crystal have also been made by using a hot-stage inside the electron microscope, and the results will be reported in another paper. MATERIAL AND METHOD A single-crystal strip of the (110) [001] orientation was prepared from a commercial grade 3 pct Si-Fe alloy by the strain-anneal technique.= The strip was approximately 0.014 in. thick, and was rolled 70 pct at room temperature to a thickness of 0.004 in. Specimens were cut from the rolled strip and were annealed in a purified hydrogen or argon atmosphere. They were then electrolytically polished in a chromic-acetic acid solution to very thin foils. Best results were found by polishing first between two narrowly spaced flat cathodes with the specimen edges coated with acid-resisting paint, followed by polishing between two pointed electrodes until a hole appeared in the center as described by Bollmann.6 It was found that a thin transparent film always formed along the thin edges of the polished specimen. This film was then removed by rinsing the specimen very briefly in a solution of alcohol with a few drops of HF or HCl. RESULTS AND DISCUSSION 1) The Deformed Crystal. From the electron-diffraction patterns taken at various areas of an as-rolled specimen, the texture components as deduced - from ordinary pole-figure analysis were confirmed. Over most of the areas where orientation was examined, a (111) pattern with a [112] direction parallel to the rolling direction was obtained. This corresponds to the main deformation texture of the (111) [112] type. In a few areas the diffraction pattern was (100) [Oil], corresponding to the minor-texture component derived from the Neumann bands. The (110) [001] orientation, which corresponds to the very weak intensity area in the pole figure, was found infrequently. A typical example of the deformed matrix having the (111) type main texture is shown in Fig. 1, where (a) is the microstructure and (b) is the diffraction pattern taken from that area. It was also frequently observed that in other areas more or less continuous rings of weaker intensity were superimposed on the simple (111) diffraction pattern, suggesting the presence of a wide range of additional orientations. Other evidence indicated that the recrystallization characteristics are different in these two different types of areas. The hot-stage observations which provide this evidence will be discussed in another paper. AS shown in Fig. l(a), numerous dislocation-free areas of very small size are embedded in the "clouds" of high-dislocation density. This indicates that the deformation of a single crystal, even after a rolling reduction of 70 pct, is far from uniform on a micro-

Jan 1, 1962

By Joseph Taylor

THE Ducktown district is in the extreme southeastern corner of Tennessee, its principal railroad point being Copperhill, on the Blue Ridge division of the Louisville &Nashville Railroad, midway between Knoxville, Tenn., and Atlanta, Ga. The ore deposits were discovered about 1849 and development work was begun in the early fifties. Only the "black copper? ores, products of secondary enrichment, from beneath the gossan outcrops and overlying the massive sulphide deposits, were then mined and smelted for their copper content. Upon their exhaustion, attention was directed to the treatment of the pyritic ore remaining, resulting in the devising of a, process consisting of open-heap roasting, followed by blast-furnace smelting, which was practised until 1903, when semi-pyritic smelting was-adopted. In 1908, the companies operating in the district; on account of litigation brought about by alleged smoke damage to forests and vegetation in the adjoining counties of Georgia, were compelled to erect enormous acid plants to prevent the escape of the sulphur dioxide produced in the smelting operations. The utilization of this sulphur dioxide in the, manufacture of sulphuric acid as a byproduct has added to the revenues of the companies, and at the same time has furnished a valuable source of supply of sulphuric acid to the fertilizer trade of the South, and more recently to the manufacturers of explosives for use in the production of war munitions. The steadily increasing demand for sulphuric acid for the manufacture of fertilizers and explosives, together with the decreasing imports of pyrites, from which the acid is generally produced, now makes it imperative that greatly extended resources of pyrite be developed. While the Ducktown deposits do not predominate in pyrite, they do contain an inexhaustible supply of pyrrhotite, admixed with pyrite, which can be satisfactorily employed to supplement or substitute for pyrite in acid making.

Jan 2, 1918