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By R. R. Klimpel Discussion by C. C. Harris, L. G. Austin

C. C. Harris (Columbia University) — The authors ' have presented relationships for the random division of a magnitude into r + l parts taking account of the order of selection. Interpreting their model in comminution terms, their Eqs. 7, 9 and 11 refer to the one-dimensional case; that is, to the subdivision of a long thin rod at random. It is assumed that the fragments may be indefinitely small. Real materials, however, are limited in the degree of subdivision which can be attained through the intervention of practical restrictions. One in fine grinding is the depletion of microflaws as material becomes finer. Another is the

Jan 1, 1969

By C. W. Phillips, R. S. Busk

WITH most cast metals the grain size may vary within wide limits, depending upon the conditions at the moment of freezing. These conditions are subject to control in magnesium-base alloys, by proper melting and superheating techniques, enabling production of quite uniform and fine-grained castings, almost independent of section thickness. However, such variations of grain size as do exist, in common with all metals, are reflected in corresponding changes in mechanical properties. It is the intent of this paper to present data giving the relationship between grain size and mechanical properties. Data are also included on the combined effects of grain size and microporosity. In addition, a short discussion of factors influencing the grain size of sand castings is included. MEASUREMENT OF GRAIN SIZE By grain size is meant the statistical distribution of volumes occupied by the individual crystallites in a metal section. Since this is almost always impossible of direct measurement, several methods of estimating and expressing the size have been evolved. Most exact methods make use of the microscope. This involves study of a single plane cut at random through the metal. What is seen in the microscope are polygons, each the cross section of a grain. The diameters or areas of these polygons are then measured and the grain size is expressed as an average diameter, number of grains per unit area, average area per grain, or, rarely, average volume per grain. Rutherford, Aborn, and Bain3 have discussed extensively the errors involved when using a plane section to estimate volume. They clearly point out that the tendency is to underestimate the true grain size because of the nature of the measurement. The A.S.T.M.. recommends that measurement be made by comparison with a standard chart, by means of Jeffries' planimetric method' or Heyn's intercept method. The Society recommends that the notation be in terms of the number of grains per unit area (as is the grain-size number used for steel) or as an average diameter, expressed in inches or millimeters (as for copper and brass). The method of measurement used for this study was comparison with a standard chart, which has been described by P. F. George.', The chart was constructed by photographing at i00 diameters a uniform specimen with an average grain diameter of 0.003 in. The average diameter of this specimen was determined by numerous measurements, using both the Jeffries and Heyn methods. The other grain sizes were then obtained by appropriate enlargement of the master sample. Careful comparison of the chart method with other methods on identical samples indicates that though the differences be-

Jan 1, 1945

By C. W. Phillips, R. S. Busk

With most cast metals the grain size may vary within wide limits, depending upon the conditions at the moment of freezing. These conditions are subject to control in magnesium-base alloys, by proper melting and superheating techniques, enabling production of quite uniform and fine-grained castings, almost independent of section thickness. However, such variations of grain size as do exist, in common with all metals, are reflected in corresponding changes in mechanical properties. It is the intent of this paper to present data giving the relationship between grain size and mechanical properties. Data are also included on the combined effects of grain size and micro-porosity. In addition, a short discussion of factors influencing the grain size of sand castings is included. Measurement OF Grain Size By grain size is meant the statistical distribution of volumes occupied by the individual crystallites in a metal section. Since this is almost always impossible of direct measurement, several methods of estimating and expressing the size have been evolved. Most exact methods make use of the microscope. This involves study of a single plane cut at random through the metal. What is seen in the microscopc are polygons, each the cross section of a grain. The diameters or areas of these polygons are then measured and the grain size is expressed as an average diameter, number of grains per unit area, average area per grain, or, rarely, average volume per grain. Rutherford, Abom, and Bain3 have discussed extensively the errors involved when using a plane section to estimate volume. They clearly point out that the tendency is to underestimate the true grain size because of the nature of the measurcment. The A.S.T.M. recommends that measurement be made by comparison with a standard chart, by means of Jeffries' planimetric method4 or Heyn's intercept method. The Society recommends that the notation be in terms of the number of grains per unit area (as is the grain-size number used for steel) or as an average diameter, expressed in inches or millimeters (as for copper and brass). The method of measurement used for this study was comparison with a standard chart, which has been described by P. F. George.5 The chart was constructed by photographing at Ioo diameters a uniform specimen with an average grain diameter of 0.003 in. The average diameter of this specimen was determined by numerous measurements, using both the Jeffries and Heyn methods. The other grain sizes were then obtained by appropriate enlargemcnt of the master sample. Careful comparison of the chart method with other methods on identical samples indicates that though the differences be-

Jan 1, 1945

As desirable as it may be to a geologist to have maximum detail in any geological report, the task of doing so for an area as vast as British Columbia within six average size magazine pages is clearly impossible. As a result, it has been necessary to draw a fairly broad picture of the geology on the following pages, but it is one which should be adequate to give the reader a concept of what rock is where in the Province. In preparing this horseback ride over the strata of the Province, much reliance has been placed on various reports appearing in trade and Canadian Government journals. Of these, one in particular stands out. Entitled "The Cordilleran Region", this report has been authored in three parts by H. S. Bostock, R. Mulligan and R. J. W. Douglas, respectively, and is included as a major chapter of the book Geology and Economic Minerals of Canada. Published in 1957 by the Department of Mines and Technical Surveys, the book has provided the extensive quotes, taken from each of the three authors, which appear on the following pages.

Jan 12, 1963

By C. K. Leith

QUOTING from Dr. Richard T. Ely:1 "Conservation, narrowly and strictly considered, means the preservation in unimpaired efficiency of the resources of the earth; or in a condition so nearly unimpaired as the nature of the case, or Wise exhaustion, admits. And broadly considered, it means more than the word itself implies, for it naturally includes an examination of methods Whereby the natural inheritance of the human race may be improved; and still more broadly considered, and as used in popular discussion, it includes a treatment of the effects of productive conservation methods upon distribution. "Conservation means a sacrifice of the present generation to the future generations Whenever it is carried too far. There is a sharp limit to the economic sacrifice that we may reasonably ask the private person to make for even the present Welfare, and the limit is still sharper when we come to consider the interests of future generations." In a paper on the iron ores of America, presented to the Pan-American Scientific Congress at Washington, I have emphasized the fact that the reserves of iron ores in the two Americas are enormously in excess of the requirements of the present generation, in fact, so large that no shortage is to be anticipated for many generations in the future; that a large part of the value of iron ores is put into them by man's efforts to make them available. This fact is fundamental for the intelligent consideration of- policies of conservation as applied to iron ore. As I interpret it, this fact makes it practically unnecessary that the present generation should make any especial sacrifice for future generations in the way of conservation of its iron-ore resources. Even if we were disposed to look forward to a period of 100 or 200 years, with a view to insuring the welfare of the people living at that time, it is doubtful whether any procedure we could now formulate would materially help them in the matter of iron ores, so large are the reserves available. In order that an appeal for conservation may be effective it must obviously favor the welfare of the present or immediately following generations; it must promise benefits to general and individual welfare during a period within the range of comprehension of the average man.

Jan 2, 1916

By B. H. Caudle, B. M. Hickman, I. H. Silberberg

Secondary recovery projects often are not started in oil reservoirs until dictated by rising GOR's or declining oil production. Such circumstances require a well dispersed injection pattern to prevent the oil bank from bypassing the production wells. Many times this purpose is served by using the five-spot or line-drive patterns, in which half of the wells are made injection wells. A regular injection pattern is proposed that is based on the same well spacing as the five-spot but in which only a third of the wells need be converted to injection wells. Fluid flow model studies on this proposed pattern show that production histories will be as good as those for a five-spot pattern at mobility ratios of three and above. The model data are presented in a form that may be used to predict recoveries from both homogeneous and stratified formations. Introduction The injection of fluid into a petroleum reservoir usually is prompted by an actual, or predicted, loss in the productivity of the reservoir. Often, an oil reservoir is produced by pressure depletion until high GOR's dictate a change in policy. Fluid injection also causes increased ultimate recovery, but this usually is of less importance to the operator than is the maintenance of the production rate. It is a fact that the ultimate recovery in any particular fluid injection project is relatively independent of the number and spacing of the injection wells as long as the reservoir voidage through the production wells is balanced by the total injection rate. However, the response of a production well is directly affected by the distance it lies from an injection well. In places where the well productivities are declining, the injection wells should be spaced as evenly as possible among the producing wells ("dispersed" injection pattern). More particularly, if the production response depends upon the formation (and subsequent production) of an oil bank, each production well should be surrounded by injection wells. Otherwise, the oil productivity will increase very little as the oil bank moves past the well.'.' An evenly spaced injection pattern has the best chance of generating an oil kick in the production wells. If reservoir voidage and injection rates are to be equal, the ratio of injection wells to production wells must be equal to the ratio of the average injectivity to the average productivity (in reservoir volumes). This ratio is in strumental in choosing the injection pattern. Table 1 shows the production well to injection well ratio for the dispersed injection patterns that have been described in the literature.'-' All of these patterns will have comparable recoveries and response times (for the same basic distance between wells). The choice of pattern there fore depends upon the relative injectivity and productivity of the wells and upon the type of drilling pattern employed. Another important factor may be the ability of the proposed production wells to make up the lost productivity from those wells converted to injectors. These factors become more pronounced at the higher oil viscosities (low gravity oils). All other things being equal, the probable ratio of single well injectivity to single well productivity will be equal to the water-oil mobility ratio of the proposed flood. Thus, high mobility ratios (due to low gravity oil) should call for fewer injection wells — as long as these injection wells are "dispersed" to obtain more even pro duction response for the remaining wells. Secondary re covery projects in oil reservoirs seldom, if ever, will have mobility ratios requiring more injection wells than production wells. Thus, only the last five of the patterns listed in Table 1 will be of significant interest in oil recovery. Almost every development drilling program calls for the wells to be drilled along equally spaced rows and

Jan 1, 1969

By C. K. Leith

Conservation, narrowly and strictly considered, means the preservation in unimpaired efficiency of the resources of the earth; or in a condition so nearly unimpaired as the nature of the case, or wise exhaustion, admits. And broadly considered, it means more than the word itself implies, for it naturally includes an examination of methods whereby the natural inheritance of the human race may be improved; and still more broadly considered. and as used in popular discussion, it includes a treatment of the effects of productive conservation methods upon distribution. "Conservation means a sacrifice of the present generation to the future generations whenever it is carried too far. There is a sharp limit to the economic sacrifice that we may reasonably ask the private person to make for even the present welfare, and the limit is still sharper when we come to consider the interests of future generations." In a paper on the iron ores of America, presented to the Pan-American Scientific Congress at Washington, I have emphasized the fact that the reserves of iron ores in the two Americas are enormously in excess of the requirements of the present generation, in fact, so large that no shortage is to be anticipated for many generations in the future; that a large part of the value of iron ores is put into them by man's efforts to make them available. This fact is fundamental for the intelligent consideration of policies of conservation as applied to iron ore. As I interpret it, this fact makes it practically unnecessary that the present generation should make any especial sacrifice for future generations in the way of conservation of its iron-ore resources. Even if we were disposed to look forward to a period of 100 or 200 years, with a view to insuring the welfare of the people living at that time, it is doubtful whether any procedure we could now formulate would materially help them in the matter of iron ores, so large are the reserves available. In order that an appeal for conservation may be effective it must obviously favor the welfare of the present or immediately following generations; it must promise benefits to general and individual welfare during a period within the range of comprehension of the average man.

Jan 1, 1916

By AIME AIME

T HE new Secretary of the Institute has been asked to address the members through the medium of MINING .AND METALLURGY, and it is perhaps well that he should do this at the first opportunity after his election. The duty of the Secretary, as the present incumbent understands it, is that of attempting to carry on the functions of the Institute in a manner that 'will tend to make it serve its most useful purpose. What is its most useful purpose or purposes? This was concisely answered by Dr. Joseph W. Richards in the June issue of MINING AND METALLURGY under the title "Why is the Institute?" And yet its most useful purposes are not 'fixed ideals or definitely determined things, they vary from year to year, changing with the development of the nation, conforming to needs and anticipating future requirements. Many men of many minds cannot always see eye to eye. The ideas or ideals of one may seem trivial to another, an obvious necessity to one is an entirely useless activity to the minds of others. A number of the activities upon which the Institute is now engaged might have been looked won, a few years since, as uncalled for, unnecessary, and un- desirable. The participation in public affairs was one of these questions. The publication of three volumes in one year may have been a questionable thing to do, but it was an achievement. A monthly magazine that will pay for itself by carrying the Institute's message to its members has its detractors, and yet to many members it seems one of those things that are quite worthwhile. Fortunately, we have a large membership, and fortunately the majority of an intelligent body of such size is apt to have in common many ideas that are right and proper. If these ideas can be ascertained

Jan 1, 1921

By M. F. McCarty, R. S. Olson

New organic flocculants of high-molecular weight are replacing lime, glue, and starch in liquid-solid separation. Of these synthetic materials, poly-acrylamides are outstanding. Polyacrylamides form a class of compounds varying widely in composition and activity. Separan 2610, one of the first of these flocculants' released to the mining industry in 1954, is described' as a high-molecular weight polymer of acrylamide with or without a copolymer material and with some replacement of amide by carboxylic groups. MECHANISM OF FLOCCULATION In practice, flocculation makes solids settle faster and filter better. But two opposing factors control it. The random motion that causes particles to collide favors Van der Waals' forces, which hold the particles together. The effect of zeta potential opposes this contact, and particles are mutually repelled. Flocculation can be achieved by reducing the magnitude of the zeta potential; this is the mechanism of flocculation by lime addition. The way in which polyacrylamides accomplish flocculation is not fully understood, but the action is undoubtedly comp1ex and probably varies considerably depending on the system. To begin with, the active groups of these compounds have an extremely high affinity for solid surfaces, probably by hydrogen bonding." Initially some active groups of the molecule attach themselves to the solids with a large portion of the molecule extending into the solution. Two particles can become tied together by long flocculant molecules in the following ways—by bonding between the active groups of two flocculant molecules on different particles, or by an extended molecule from one particle attaching itself directly to the surface of the other particles." These flocculant bridges prevent the particles from moving apart through random motion, but when such motion moves them together other active groups on the flocculant bridge bond to the solids, holding them in the closer position. This process is repeated until the particles are close together. Although bridging is probably a major flocculation mechanism, it is not the only phenomenon involved. Relatively neutral acrylamide flocculants reduce the magnitude of the zeta potential by increasing the viscosity of solution in the immediate vicinity of the solid surface which contains the mobile counter ions of the double layer. In other words, it moves the shear surface which bounds the zeta potential out into the solution containing counter ions which tend to neutralize the zeta potential. This effect is probably more pronounced during the initial adsorption period, before the flocculant molecules are pulled close to the solid. In some cases the slight charge of the polyacry-lamide molecule tends to neutralize a zeta potential. However, this is not a primary flocculation mechanism, as evidenced by the fact that the polyacrylamides will flocculate solids with either positive or negative zeta potential. Adsorption of polyacrylamide flocculants by a solid is substantially an irreversible reaction. Since the flocculant molecule is attached to the particle surface by many active groups of high bonding strength, desorption would require the simultaneous breaking of many bonds—an unlikely occurrence. UNIQUE PROPERTIES The irreversible adsorption of certain polyacrylamides, the flocculant's high affinity for solid surfaces and its rapid adsorption make it effective, but these unique properties require special techniques to achieve maximum flocculation. If flocculants of this type are added to a pulp as a relatively concentrated solution, the solids in the

Jan 1, 1960

By Harvey T. Kennedy, Erasmo T. Guerrero

In this investigation, the effects of the surface tension of brine and the interfacial tension between oil and brine on the recovery of oil by water flooding of Woodbine sand were studied. Variation of the surface forces was obtained by the addition of small amounts of commercially available chemicals, which did not appreciably change the surface tension of the oil. Fourteen surface-active agents, which were found to be effective in lowering the surface and interfacial tensions, were further investigated to determine the extent of their adsorption by the Woodbine Sand cores. It was found that adsorption was sufficient in all cases to prevent any substantial concentration of chemical at the flood front. The flow system was, therefore, brought to equilibrium with definite concentrations in the flood water by circulation before each test. The data thus have no relation to the results obtainable by using the chemicals in full-scale water floods, but should be helpful in predicting the performance of surface-active chemicals which are not lost by adsorption, if such can be found. Flow tests were made on various concentrations 01 six chemicals selected from the 14 investigated for surface activity and adsorption, with and without the presence of gas in the core. It was found that lowering the interfacial tension had a tendency toward reducing the recovery of oil and that the reduction of the surface tension of the brine had little or no effect. A substantial beneficial effect, however, resulted from the presence of gas in the cores. INTRODUCTION The movement and distribution of crude oil in a porous medium are governed by such factors as surfacc and interfacial tensions, viscosity of the oil, pore size configuration, and wetting characteristics of the medium. The knowledge of the part played by each of these factors is limited. If the oil is assumed to be distributed in droplets whose movement is restricted only by the pore openings, the following equation may be applied: ?P= 2r(1/r1-1/r2) .......(1) In this equation ?P is the pressure drop necessary to force an oil droplet through the construction, r is the oil-brine interfacial tension, r1 is the radius of curvature at the forward and smaller end of the deformed droplet, and r2 is the larger radius. This equation neglects the effects of viscosity, as a static or near static condition is assumed. It would apply equally well for a bubble of gas in liquid if r were taken as the surface tension of the liquid. This relation shows that droplets can be more easily displaced if the interfacial tension is decreased. The displacement of oil from the surface of a sand particle may also be considered from the basis of selective wetting assuming that the oil droplets are smaller than the pore constructions and that the sand surfaces may be considered as planes. A relation of the forces involved can be derived from Dupre's equation to give: Wos = row (1 +Cos?)........(2) where Wos = Work of adhesion between the sand and the oil row = Oil-water interfacial tension 0 = Contact angle ros = Oil-solid interfacial tension This equation would indicate that the displacement of oil from a sand surface is more readily obtained when the water-oil interfacial tension is reduced provided the contact angle remains constant. Evidently. however, the values of Cos 0 may vary along with the water-oil interfacial tension due to changes in the other surfaces of the system. The above theoretical considerations suggest that perhaps even the static behavior of a dispersed oil phase in a porous medium is considerably more complex than may be inferred by the simple systems

Jan 1, 1955

By Louis R. Hodell

WHEN the drilling of an oil well is completed a permanent opening from the reservoir to the surface must be provided. This is done by lining the hole with pipe, commonly known as casing. In the past, all but a small amount of casing has been run in the hole and joined by threads and couplings. Recently, however, in California, Texas, and Oklahoma, there has been a definite tendency 'to adopt -the welded joint for the following reasons: (1) Plain end casing for welding may be bought for 15 per cent less than thread-and-coupled casing; some of this is offset by the cost of welding the pipe in the hole but a respectable net profit remains.

Jan 1, 1937

By Paul B. Crawford, Melvin B. Burton

A procedure is given which describes how the gelatin model may be-used to study the effect of mobility ratio on areas swept before and after breakthrough in fluid injection programs. Differences in mobility ratio are achieved through the proper selection of electrolytes for the invading and displaced fluids. The progress of the front is followed visually and photographed or traced onto plates (it desirrd positions before and after breakthrough. Example applications to standard flooding pattrrrls, vertically and horizontally fractured reservoirs and the in-situ combustion recovery process ore presentrtl. INTRODUCTION In water flooding, gas cycling and other fluid injection programs, the sweep efficiencies and swept areas after breakthrough are known to depend on the mobility ratio. Previous investigators have described the application of the X-ray technique, stepwise use of the poten-tiometric model and numerical procedures for studying these problems.1,3,4,6 Others have described the application of the electrolytic and gelatin models for studying sweep efficiencies at a mobility ratio near one.2,5,7,8,9 It is a purpose of this paper to describe a procedure for using the gelatin model to study swept areas at mobility ratios other than one. PROCEDURE The technique developed for gelatin model studies is composed of four phases: the construction of the model, the selection and preparation of electrolytes, the running procedure, and the recording of the swept areas. Each phase is discussed independently in order that the over-all procedure will not be confused. Construction of the Model Since some of the advantages of the gelatin model are its economy, and speed, it is desirable to have as small a model as is possihle without creating error through the inability to follow visually the progress of the colored front. For this work, it was found that a distance of 4 to 6 cm between salt bridges is convenient to use. Since the size is relatively small, it follows that the gelatin layer must be thin. For this study, 1/8 in. was used as the gelatin thickness in each case. The model was constructed on a flat 1/2-in. plastic (Lucite) base with boundaries constructed from 1/8-in. plastic strips. The well pattern to be studied was outlined with the 1/8-in. plastic strips on the base with narrow apertures (- - 2 mm) in the boundary to represent the wells. Behind each well opening, a rectangular area of some 8 to 12 sq cm was outlined by additional plastic strips. The plastic strips were fastened to the base by any suitable non-conducting cement so that the boundary system was liquid tight. The electrodes were constructed from sheet copper in a fashion that would allow easy removal. In this work, it was found that by simply forming a large U-shaped clip from a strip of the copper that would slip over the boundary was satisfactory and easily removed. The electrodes should be as wide as one of the sides of the rectangular area behind the well opening. If a fractured pattern is studied, fractures inside the well pattern may be represented by strips of copper of the desired shape mounted in some easily removable fashion. The reason that apertures (or salt bridges) were used for wells instead of metallic electrodes is that the plating of the electroactive ion at the cathode and the introduction of an electroactive ion at the anode has a detrimental effect on the swept area outline if these operations \rere permitted to be carried on within the well pattern itself. The anode may be used within the well pattern

Jan 1, 1957

By M. C. Smith, W. V. Green, D. M. Olsen

The creep-rupture behavior of commercial powder-metallurgy molybdenum rod is reported in the temperature range 1600" to 250O°C, at stresses up to 9000 psi and times up to 1 month. The effects of temperature, stress, and grain growth are discussed. Rupture time is fitted to the Larson-Miller parameter and compared to lower-temperature and higher-stress results reported by pugh.1 BECAUSE of its high melting point, molybdenum should retain useful strength to relatively high temperatures. Combined with its ready availability in the United States, this makes it attractive for many applications in missiles, rockets, and so forth—wherever its susceptibility to oxidation can be tolerated or overcome. The mechanical properties of molybdenum rod in the temperature range —200" to 1540°C have been reported by pugh,' Bechtold,' Parke,3 and Carriker and Guard.4 Madden and chen5 have measured the tensile properties of molybdenum single crystals in vacuum up to about 2500°C. As one further step in evaluating its mechanical usefulness, the constant-load creep-rupture properties of commercial powder-metallurgy molybdenum rod have been investigated in the range 1600" to 2500°C. MATERIAL TESTED Creep specimens were machined from 1/2-in. round commercial molybdenum rod, manufactured from powder by pressing, sintering, and swaging. Spectrochemical analysis of the rod showed "traces" (less than 0.01 pct) of silicon, aluminum, chromium, iron, and zirconium, and "faint traces" (less than 0.001 pct) of manganese, magnesium, cobalt, and nickel. Carbon content was 130 to 200 ppm, nitrogen was 110 to 180 ppm, and oxygen 30 to 35 ppm. A typical microstructure of the as-received rod is shown in Fig. 1. Room temperature tensile properties for five specimens strained at about 0.015 in. per in. per min are shown in Table I. CREEP SPECIMENS USED The specimens used for creep-rupture testing are illustrated in Fig. 2. The 1/4-in.-diam gage section was 3/4 in. long, and terminated at shoulders 5 mils high. These shoulders served as fiducial marks for optical strain measurements. Surface finish on the gage section was 16pin. r.m.s. One specimen, for a "long-time" test described below, was modified by dividing the 3/4-in. gage length into three 1/4-in. long sections with individual diameters of 0.250, 0.230, and 0.210 in., each terminating in a pair of fiducial shoulders. TESTING PROCEDURE The constant-load creep-testing machine used has been described by Smith, Olson, and Brown.6 In it the specimen is held vertically on the axis of a cylindrical tantalum or tungsten heater tube by threaded molybdenum or tungsten grips. Both specimen and grips are heated by radiation from the heater-tube, which is heated by its own electrical resistance. The bottom specimen grip is held at its lower end by a clevis pin. The testing load is applied to the specimen through the upper grip by means of hanging weights, a constant force-multiplication lever system, and a pull rod sealed to the chamber lid by a bellows. The incandescent specimen is viewed by an external optical system through slots in the heater-tube and radiation shielding, and an enlarged image of it is projected on a ground-glass screen. Gage-length measurements are made on this image with a pair of cathetometers. Thorium oxide coatings were applied to the threaded ends of most specimens, to prevent diffusion-welding of specimens to grips during testing. Without such a coating welding usually occurred, and grips were often broken by subsequent efforts to remove the tested specimens.

Jan 1, 1960

By H. L. Washburn, G. L. Judy

DURING recent years thermal drying of fine coal has increased at a tremendous rate, but very little discussion of the several excellent units has found its way into print. This is particularly true for operating and maintenance costs, and the operator who is faced with his first fine coal drying installation must depend chiefly on hearsay when trying to determine what his drying costs will be. This article presents the maintenance and operating costs for the seven drying units now installed in preparation plants of Pittsburgh Consolidation Coal Co. and lists other cost information that should be obtained before any particular drying unit is selected. Plant Description: The fine coal drying section of Plant A consists of four Flash driers operating on two furnaces equipped with spreader stokers. Plant B has one Flash drier operating (together with a screen-type coarse coal drier) on one furnace equipped with a spreader stoker. Plant C has two Cascade-type driers operating on a single furnace with a spreader stoker. Plant Costs: Tables I, 11, and III present the cost of operating these units as reported by the individ- ual plants. As can be seen, the labor rates vary, depending on the amount of overtime paid and the time interval the cost figures cover. There is considerable variation in thermal units used and in the value given to the thermal units at the particular mine. There is some difference in power costs at a given location and, finally, the power costs of conveyors leading to the drying plants were included in some cases. Maintenance supply costs are simply a tabulation of the cost of all supplies used on the driers, furnaces, and stokers. Depreciation is not included, and the tables omit items such as supervision, plant cleanup, oiling, general maintenance, taxes, and insurance. These tables in themselves do not offer a true comparison of costs. This information must be reduced to some common basis. But what is this common basis to be? A mine operator must calculate his overall mine and preparation plant costs in terms of tons of clean coal sold. Unit costs on pieces of equipment within a given plant are correctly calculated on the same basis. However, when unit costs are compared between one plant and another, some thought must be given to unit design. This reasoning is similar to the old argument concerning i solid bowl vs basket-type centrifuges—the units themselves are not directly comparable without their supporting equipment. So it is with thermal driers. Except in rare cases of low entering moisture i content, driers are sized on the basis of water that must be evaporated, while the wear each unit gets de-

Jan 1, 1958

By P. R. Gage, R. W. Bartlett

At high temperatues and reduced oxygen pressuves, molybdenum silicicles oxidize to form SiO(g) vathev than a passivating SiO2 film. This is a sevious problem for low-pressure applications of sili-cide-coated rejvactory tnetals. As oxiclalion pvoceeds, the higher oxidntion potential of silicon initially suppresses oxidation of molybdenum and silicon is depleted near the surface. Eventually, silicon depletion causes secondary passivation (SiO2) mid an active to passiue transition in oxidntion behavior at moderately low pressures. At very low pressures, silicon depletion continues until steady-state oxidation of both silicon and rnolyhdenum can proceed at rates propovtional to their initial stoicliiorrzetvies. Ohsel-vations of 'oxidatiou-rate belzcriliov at temperatures from 1101° to 1700°C and oxygen pressures from 10-7 to 1 at in were made using thermogravimetn'c, X-ray diffraction, and elect?*on-rtric?ro/,vobe techniqrres. The experimental results are in good agreement with calculated lirnits for the various types of behavior that were based on tlievtnochernicnl atzd dffusion rate data for the Mo-Si system. A protective oxide film normally forms during the oxidation of elemental silicon. However, at elevated temperatures and reduced pressures this film is not present and oxidation is rapid. wagnerl has shown that this behavior occurs because SiO(g) is more stable than SiO2. The behavior of the silicides at high temperatures is similar but more complicated. Molybdenum and several silicide compounds are involved and the chemical activity of silicon, or the equivalent silicon vapor pressure, can vary considerably in these phases. Also, diffusion in the silicides resulting from reactions in which a higher silicide is reduced to a lower silicide, or molybdenum containing dissolved silicon, must be considered. EXPERIMENTAL AND ANALYTICAL METHODS Isothermal oxidation experiments were conducted using hot-pressed MoSi2 and Mo5Si3 wafers. Each experiment was conducted at a fixed oxygen pressure by controlling the flow of oxygen in and out of the furnace chamber. Most of the experiments were conducted in a molybdenum-wound tube furnace. Special construction features, including use of a high-purity dense A12O3 refractory tube, permitted operation in high vacuum to 1500°C. Higher temperatures could be obtained at higher working pressures and with a sacrifice of tube lifetime. Temperature was measured with three Pt 6 pct Rh/Pt 30 pct Rh thermocouples and controlled with a proportional controller. Weight changes were monitored with a quartz spring balance. The few experiments, at higher temperatures and low pressures, were conducted in a cold wall vacuum chamber using induction heating with direct susceptance of the sample. Because of the variable levitation effect of the induction coil on the sample, weight changes could not be monitored continuously in these experiments. All samples representing both experimental methods were weighed before and after oxidiation and examined with a microscope and analyzed by X-ray diffraction. The analytical treatment assumes equilibrium at interfaces and uses existing thermodynamic data. For convenience, equilibria are expressed as chemical potentials or as vapor pressures of the gases involved. The resulting differences in equilibrium vapor pressure between adjacent interfaces and between the surface and external atmosphere drive diffusion processes in the solid and gas boundary film, respectively. These diffusion processes govern the rate of oxidation. A bibliography of the sources of thermochemical data for the reactions pertinent to the Mo-Si-O system is given in Table I. Reactions are listed with the sources of free-energy data referenced. Since all of these reactions involve one or more gas species, usually oxygen, a plot of the product-gas chemical potential, -RT In Pg, vs absolute temperature for each reaction is given in Fig. 1. These curves can be used to determine equilibrium vapor pressures or to compare the stability of different compounds in the various gases: O2, Si, SiO, and Moo3,. The data of Table I and Fig. 1 were used to determine the analytical results presented in this paper. EXPERIMENTAL RESULTS The weight changes for three MoSi, samples oxidized at 1500°C are plotted against time in Fig. 2. The treatments were identical except for the indicated variance of oxygen pressure and each curve represents one of three characteristic types of behavior that were observed. The upper curve is an example of passive oxidation, which is defined as

Jan 1, 1965

By K. L. Williamson, P. W. Dugan

INTRODUCTION In recent years there has been increased social awareness and government attention directed toward the mining industry. The growing influence of the Occupational Safety and Health Administration (OSHA), the Mine Safety and Health Administration (MSHA), and the Environmental Protection Agency (EPA) has resulted in volumes of regulations governing a multitude of health and safety aspects of mining and milling. These regulations naturally have had an impact on new plant design and in some cases have necessitated retrofitting of existing plants. This paper will not examine the regulations governing the industry, since they are a matter of public record, but rather will address two specific health considerations, dust and noise, and their influence on the design of crushing and screening plants. DUST AND NOISE CONCEPTS Dust is generally defined as finely divided solids which may become airborne without any physical or chemical change except fracture. Since the purpose of comminution circuits is to reduce the size of solids by fracture, a percentage of the material is normally reduced in size to a point where it can easily become airborne. The major cause of dust becoming airborne is the air induced by falling material. When granular material falls through a distance, the induced (or entrapped) air rushes out available openings, carrying with it the fine particles that have become suspended. For this reason, the major points of dust generation are the points where the material is falling: chutes, transfer points, screens and equipment feed and discharge points. The expected dust concentration in an area is a function of the degree of size reduction (i.e., finer particles are more readily carried by air currents than heavier particles) and the volume of air that is induced. The measured dust concentration values for various operations agree with this

Jan 1, 1982

By C. G. Dunn, F. Lionetti

The energy associated with grain boundaries in polycrystalline aggregates is believed to play a major role in grain growth processes and, when growth ceases, to determine the final equilibrium grain boundary angles. Further, the energy of grain boundaries of recrystallization nuclei is a factor in nucleation processes. It is important to know, therefore, how the energy per unit area of a grain boundary, that is, the grain boundary surface tension y, depends on the difference in orientation of the two lattices of the grains producing the boundary. Although the problem is important, surprisingly little has been done toward a quantitative evaluation of the effect of orientation difference on grain boundary energies. C. S. Smith1 recently has discussed this problem and in addition to showing effects of orientation difference on equilibrium angles has shown a variety of interesting effects of surface tension on the appearance of microstructures. Fig 1 and the following relations expressed in Eq 1, which connect equilibrium grain boundary angles and surface tensions, illustrate equilibrium conditions which are believed to hold true in metals. ?l2 _ ?23 _ ?l3 [1] sin ?3 sin ?1 sin ?2 Clearly any two of these surface tensions can be expressed in terms of the third when the equilibrium angles ?1, ?2, and ?3 are known. Applied to the present problem for solid state equilibrium of three grains, the angles ?1,?2 and ?3 must be measured in a plane perpendicular to the line of junction of the three grains. Normally a direct determination of these angles from random microsections is impossible. Consequently Harker and Parker2 and Smith1 (except for some measurements on flat specimens) resorted to a statistical method to determine equilibrium grain boundary angles. Smith reported that grain boundaries meet the surface of a piece of metal nearly perpendicularly. He reported also, in connection with direct angle measurements on flat specimens with grains extending through the thickness, that angles varied appreciably from 120" and concluded that there was a measurable effect of orientation difference on surface tension. Another direct way of determining equilibrium angles and a method adaptable to studying particular configurations, recently suggested by Dunn,³ is to use a three-grain flat specimen with orientations of grains so chosen that the junction line of the three grains will be straight throughout the thickness and perpendicular to the surface of the specimen. Choice of orientations is possible when individual grains of each group can be grown to predetermined orientations through the reorienting and growth of " seed crystals " as described.³ Not only is it possible, for example, to have grains with the same crystallographic plane in the plane of the specimen, but a given orientation difference between two grains can be made a common factor to an unlimited number of three-grain groups while a series of orientation differences is investigated. Any effect of anisotropy of gas-solid surface tension due to grain orientation should be minimized by having all gains oriented the same with regard to crystallographic plane in the plane of the specimen. Another feature of the three-grain group is the notched grain boundaries as shown in Fig 2 for one specimen (S4). The notches serve to anchor the end positions of the grain boundaries (especially at high temperatures) while the central and junction point of the grains moves toward an equilibrium position. Final equilibrium should produce straight grain boundaries if the notches are very narrow and if changes in orientation* of the grain boundary do not alter the surface tension.† If one assumes the straight line condition and no change of surface tension with small changes in grain boundary orientation and finds the equilibrium configuration by a minimization of the grain boundary energy, one obtains the relations given in Eq 1. The approach to straight line boundaries or to minimum energy configurations in specimens containing large grains, such as those used in the present investigation, may be very slow compared with the approach to equilibrium conditions for the grain boundary angles. It may be desirable, as proved to be the case in the present investiga-

Jan 1, 1950

By Merlon C. Flemings, Theodoulos Z. Kattamis

Examination was made of the distribution of tnanganese and nickel in colutrrnar dendrites of a cast low-alloy steel; more limited work was corzducted on chromium. Corresponding "segregrction ratios" were calculnted and shown to be relntivelv insensitive to cooling rate (''segregation ratio" is defined (Is the ratio of maximum to minimum concentrations within a volume whose dimensions are the order of the dendrite-arm spacing). Isoconcentratiorl curves were determined by the electron micropvobe and by rt7etallografihic studies on specimens subjected to isothermal-transformation treatments. From construction of isoconcentration curves, morphology of columnar dendrites is descvibed as intermediate between Perfect rodlike and sheetlike morphologies. The study is extended to equiaxed dendrites and it is shown that the strcture of these dendrites is sittlilar in many respects to that of columnar dendrites. On the basis of tlze sheetlike morphology of dendrites, a simple model is pvoposed for calculation of honzogenization kinetics. Results of trzatllevlatical analysis brcsed on this utzodel are given. This analysis relates residual segregation to time at homogenization temperature; it is in agreement with experiment. Calculations are given which show that even for relatively rapidly cooled material (of 1-ine dendrite-artn spacing) treatmets at 1200°C or above are necessary to achieve slgxificant Izomogenization of elenlents other than carbon itz reasonable time (e.g., rnangclnese, nickel). Conlplete homogenization of carbon is obtnined at much lowev tenlperatures (below 870°C). IN dendritic solidification of castings and ingots, solute redistribution during freezing results in mi-crosegregation of most alloy elements. The micro-segregation is such that minimum solute concentrations occur at the center of dendrite arms and maximum concentrations occur between dendrite arms. Residual segregation after subsequent therma1 processing (homogenization) depends on maximum and minimum initial concentration, on the detailed geometry of the isoconcentration surfaces within interdendritic regions, on the diffusion coefficient of the solute, and on time of thermal processing. The objective of this work was to determine, for a low-alloy steel, maximum and minimum concentrations, and the geometry of isoconcentration surfaces, primarily in order to permit calculation of homogenization kinetics. Most of the work reported was conducted on Samples from a unidirectionally solidified, fully columnar ingot. This type of ingot is made by extracting heat during solidification from one face; techniques for accomplishing this have been discussed.' Samples were taken at several locations, up to 5.75 in. from the mold chill face; the bulk of the work was performed on samples at 5.75 in. Alloy cast was, nominally, 0.4 pct C, 1.8 pct Ni, 0.8 pct Cr, 0.7 pct Mn, 0.25 pct Mo, 0.3 pct Si, and the balance iron. Brief study was also made on samples from an ingot which solidified with equiaxed grain structure. SAMPLE PREPARATION AND ANALYSIS Samples for electron-microprobe analysis were incorporated in mounts that included pieces of electrolytic nickel, chromium, and manganese, in order to normalize the intensities of these solutes in the specimens; also, a piece of electrolytic iron was included to measure the background. All specimens were polished in the usual metallographic manner. After the microprobe traces were made, the path was revealed by etching the specimens with picral. All microprobe analyses were made by point counting, integrating for 30 sec. The distance between points was fixed from 2 to 10 p, according to the precision desired in each case, the fineness of the structure, and the concentration gradient existing in a given area. (The distance was chosen 2 to 5 p near the maximum-concentration regions and 5 to 10 p near the minimum concentration.) The "take-off" angle for the A.R.L.-Model No. 21000 microprobe employed was 52.5 deg. Samples for metallographic analysis of isoconcentration curves were prepared by austenitizing at 1540°F for 20 min, quenching to the nose of the TTT curves (1200°F), heat treating isothermally at this temperature for a given time 0, and then quenching to room temperature. Due to concentration gradients existing in a dendritic structure, no transformation will take place for a given time 0 of isothermal heat treatment in the regions where the a.lloy concentration is higher than a given limit. Thus, the dendrite appears limited by an isoconcentration curve and can be made to appear to grow by varying the time of isothermal heat treatment.

Jan 1, 1965

By E. E. Donath

Application of the coal hydrogenation process for the production of chemicals is described. It has been estimated that a plant to produce 31,090 bbl per day of chemicals and fuels would cost $326,- 000,000. These products would consist of 6.1 pct by weight tar acids, 50.8 pct aroma tics, 16.4 pct LPG, and 26.7 pct gasoline. THE coal hydrogenation process is well known as a means for the production of liquid fuels from coal. In this paper the possibilities of the coal hydrogenation process as a source of chemical raw materials will be discussed. The recovery of chemicals from coal hydrogenation products necessitates some modifications and additions to the equipment used for the production of fuels. The conversion of coal into liquid fuels such as gasoline requires two steps: liquid phase and vapor phase hydrogenation. Intermediate oils obtained in the liquid phase contain oxygen and nitrogen compounds, especially aromatic compounds, since the coal itself is composed mainly of cyclic compounds. These oils are the raw material for the separation of high molecular weight aro-matics and of tar acids and tar bases. The relative amounts of heavy and middle oil—boiling above and below, e.g., 325°C—can be influenced by temperature, residence time, and catalyst of the liquid phase hydrogenation. In the vapor phase hydrogenation a solid bed catalyst is used to convert the intermediate oil from the liquid phase operation into hydrocarbons of the gasoline boiling range. Essentially pure hydrocarbons with a low content of sulphur, oxygen, nitrogen, and olefines are obtained. Depending mainly on the catalyst, the high ring compound content of the liquid phase oil can be preserved and gasoline rich in aromatics obtained. However, with other catalysts, these ring compounds can be split into gasoline with a high content of isoparaffins.' Again, depending on the operating conditions, products of varying boiling range can be obtained. Selection of catalyst and operating conditions therefore makes possible the production of different grades of motor fuel and also variations in the relative amounts of benzene, toluene, and xylene when aromatic hydrocarbons are produced. The schematic flowsheet, Fig. 1, shows the main steps of the coal hydrogenation process, and the product streams used for the recovery of chemicals are indicated. In the liquid phase hydrogenation stage, coal is made into a paste with recycle heavy oil. The coal paste is mixed with hydrogen and preheated at a pressure of 300 to 700 atm in heat exchangers and preheaters. The coal paste and hydrogen enter high pressure converters where the liquefaction of coal, conversion of the high boiling liquid materials initially obtained, into intermediate oils is performed at a temperature around 470°C. The reaction products enter the hot catchpot in which lower boiling oil vapors are separated from the residue containing unreacted coal, ash, and heavy oil. This residue, usually called H.O.L.D. (heavy oil let down), is processed to separate solid and liquid material. By thermal treatment of the residue, e.g., a coking process, distillate oil is obtained, which can be recycled as part of the pasting oil. This stream is rich in polynuclear aromatics and can be, and has been, used for the recovery of such material. The oil vapors and hydrogen from the hot catchpot are cooled in heat exchangers and a cooler, and the condensed oil is separated from the recycle hy-

Jan 1, 1953

By E. E. Donath

Application of the coal hydrogenation process for the production of chemicals is described. It has been estimated that a plant to produce 31,090 bbl per day of chemicals and fuels would cost $326,- 000,000. These products would consist of 6.1 pct by weight tar acids, 50.8 pct aroma tics, 16.4 pct LPG, and 26.7 pct gasoline. THE coal hydrogenation process is well known as a means for the production of liquid fuels from coal. In this paper the possibilities of the coal hydrogenation process as a source of chemical raw materials will be discussed. The recovery of chemicals from coal hydrogenation products necessitates some modifications and additions to the equipment used for the production of fuels. The conversion of coal into liquid fuels such as gasoline requires two steps: liquid phase and vapor phase hydrogenation. Intermediate oils obtained in the liquid phase contain oxygen and nitrogen compounds, especially aromatic compounds, since the coal itself is composed mainly of cyclic compounds. These oils are the raw material for the separation of high molecular weight aro-matics and of tar acids and tar bases. The relative amounts of heavy and middle oil—boiling above and below, e.g., 325°C—can be influenced by temperature, residence time, and catalyst of the liquid phase hydrogenation. In the vapor phase hydrogenation a solid bed catalyst is used to convert the intermediate oil from the liquid phase operation into hydrocarbons of the gasoline boiling range. Essentially pure hydrocarbons with a low content of sulphur, oxygen, nitrogen, and olefines are obtained. Depending mainly on the catalyst, the high ring compound content of the liquid phase oil can be preserved and gasoline rich in aromatics obtained. However, with other catalysts, these ring compounds can be split into gasoline with a high content of isoparaffins.' Again, depending on the operating conditions, products of varying boiling range can be obtained. Selection of catalyst and operating conditions therefore makes possible the production of different grades of motor fuel and also variations in the relative amounts of benzene, toluene, and xylene when aromatic hydrocarbons are produced. The schematic flowsheet, Fig. 1, shows the main steps of the coal hydrogenation process, and the product streams used for the recovery of chemicals are indicated. In the liquid phase hydrogenation stage, coal is made into a paste with recycle heavy oil. The coal paste is mixed with hydrogen and preheated at a pressure of 300 to 700 atm in heat exchangers and preheaters. The coal paste and hydrogen enter high pressure converters where the liquefaction of coal, conversion of the high boiling liquid materials initially obtained, into intermediate oils is performed at a temperature around 470°C. The reaction products enter the hot catchpot in which lower boiling oil vapors are separated from the residue containing unreacted coal, ash, and heavy oil. This residue, usually called H.O.L.D. (heavy oil let down), is processed to separate solid and liquid material. By thermal treatment of the residue, e.g., a coking process, distillate oil is obtained, which can be recycled as part of the pasting oil. This stream is rich in polynuclear aromatics and can be, and has been, used for the recovery of such material. The oil vapors and hydrogen from the hot catchpot are cooled in heat exchangers and a cooler, and the condensed oil is separated from the recycle hy-

Jan 1, 1953