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By H. V. Churchill

There are two distinct methods of combating corrosive conditions. The first and most popular method is to choose a surface or material which will give adequate service under the specific and general conditions which are present. The second is a control or modification of the corrosive conditions to the end that metals and materials which would be attacked and corroded without such control or modification may be used. Under the first method of attack of the corrosion problem may be grouped such devices as the selection of metals or alloys which offer great resistance or the use of protective coatings such as paints, lacquers or metallic coatings. Such procedures are exceedingly useful. It is undoubtedly true that most of the problems of corrosion will be solved by recourse to this first method of attack. However, it must be remembered that there are many conditions in which metals are used where the choice of the particular metal to be used must depend upon other factors than corrosion behavior. Some of the factors which may govern the selection of metals for specific use are the physical and mechanical properties of the metals. But there is another factor which is of prime importance and that is relative price. It is the pressure of these factors of mechanical properties, physical characteristics, and relative price that has acted as the stimulus for the second methhod of combating corrosion. The producer and user of various metals is confronted with the fact that because of mechanical properties, physical characteristics, or price, the use of a particular metal is desirable even though the corrosion conditions are adverse to the use of the metal. In many cases, the successful use of the metal may be made even though it is impossible to protect the metal by coatings. This is rendered possible by control or modification of the corrosive media. Use of Sodium Silicate to Prevent Attack by Alkali Solutions This idea of controlling or modifying corrosive media is well illustrated by some recent experiences with aluminum. For a number of years collapsible tubes have been made of aluminum. Due to the ease with which aluminum is attacked by even mild alkalies, the use of such tubes

Jan 1, 1929

By H. V. Churchill

There are two distinct methods of combating corrosive conditions. The first and most popular method is to choose a surface or material which will give adequate service under the specific and general conditions which are present. The second is a control or modification of the corrosive conditions to the end that metals and materials which would be attacked and corroded without such control or modification may be used. Under the first method of attack of the corrosion problem may be grouped such devices as the selection of metals or alloys which offer great resistance or the use of protective coatings such as paints, lacquers or metallic coatings. Such procedures are exceedingly useful. It is undoubtedly true that most of the problems of corrosion will be solved by recourse to this first method of attack. However, it must be remembered that there are many conditions in which metals are used where the choice of the particular metal to be used must depend upon other factors than corrosion behavior. Some of the factors which may govern the selection of metals for specific use are the physical and mechanical properties of the metals. But there is another factor which is of prime importance and that is relative price. It is the pressure of these factors of mechanical properties, physical characteristics, and relative price that has acted as the stimulus for the second methhod of combating corrosion. The producer and user of various metals is confronted with the fact that because of mechanical properties, physical characteristics, or price, the use of a particular metal is desirable even though the corrosion conditions are adverse to the use of the metal. In many cases, the successful use of the metal may be made even though it is impossible to protect the metal by coatings. This is rendered possible by control or modification of the corrosive media. Use of Sodium Silicate to Prevent Attack by Alkali Solutions This idea of controlling or modifying corrosive media is well illustrated by some recent experiences with aluminum. For a number of years collapsible tubes have been made of aluminum. Due to the ease with which aluminum is attacked by even mild alkalies, the use of such tubes

Jan 1, 1929

By C. M. Young

Bituminous coal piled in heaps or bins frequently undergoes a process of spontaneous heating as the result of the absorption of oxygen. It seems probable that the first absorption of oxygen by coal which has not previously been exposed to the air may occur as a condensation or a combination of oxygen in some form which does not result in the production of carbon dioxide, but slow combustion soon begins. The absorption of oxygen is accompanied by an increase of temperature, and this by an increased rapidity of absorption; hence the dangerous condition proceeds from bad to worse, until the kindling point is reached, unless the process is interrupted. A dangerous rise of temperature can be prevented by excluding oxygen, by increasing the bulk of coal in proportion to its surface exposed, or by circulating enough air to dissipate the heat produced. The storage of coal, in practice, varies from almost complete exclusion of oxygen, by storing under water, to such freedom of access as exists when the coal is stored in open piles. Oxygen available for absorption by coal is supplied by the air in the interstices between lumps and by additional air which may enter the pile through circulation. The size of the coal largely affects both of these supplies; for if the fragments are small the spaces between them constitute a small percentage of the total volume, and little oxygen will be available unless the circulation of air brings in a fresh supply, while with large fragments the percentage is relatively large; circulation also is much easier through a pile of coarse lumps. In the case of lump coal, although a large amount of air may be present, the exposed surface is comparatively small and there is little opportunity for the absorption of oxygen to be so rapid as to cause dangerous heating. Attempts have been made to prevent heating by allowing a sufficient circulation of air to carry off the heat generated; obviously this method cannot be applied to fine sizes nor mixed sizes. When storing coal at the University of Illinois, an attempt has been made to use so much fine coal and to pack it so thoroughly as to prevent circulation of air, while also reducing the original air in the pile so as to prevent heating. This method has been fairly successful, but in some

Jan 1, 1918

By Robert B. Bossler, Parke A. Dickey

The presence of connate water in oil sands is of far greater practical significance in secondary oil-recovery operations than it is in primary operations. The percentage saturations of oil, water, and gas in a depleted field determine whether it will be economically possible to recover oil by secondary methods, and whether water-flooding or gas-driving, or either, will be successful. It is suggested that economic recovery of oil by secondary water-flooding can occur only when a rich bank of oil is formed by the encroachingm water. If the sand has a greater effective permeability to water than it has to oil before flooding, a bank will not be formed, and water-flooding will not be successful, although gas-driving may be. Published results of laboratory work indicate that the effective permeability of a sand to oil and water depends primarily on the saturation of the sand by these phases. They also indicate that a small difference in relative saturation produces a large difference in effective permeability to the phase in question. There thus exists a critical range of saturations, wherein a small change in oil and water content of the sands will make water-flooding possible or impossible. In gas-drive operations the water saturation is less critical but no less important. The presence of connate water in a sand increases the proportion of the residual oil that may be recovered by gas drive. Sands containing oil saturations too low and water saturations too high to make water-flooding possible can often be subjected to gas drive with economic recovery of oil. The results of laboratory work on test samples that do not contain water cannot be applied to normal field operations. More tests on cores containing water as well as oil are desirable, and the improvement of coring technique is necessary. However, sufficient data are already available to enable an operator to use core data intelligently in estimating the chances of a secondary oil-recovery program. Introduction In recent years laboratory work has led to a much better understanding of the principles of oil-reservoir performance. The general principles of the expulsion of oil from sandstone by gas or water were developed by geologists of the Second Geological Survey of Pennsylvania in the 1870lsl but only recently has the mechanism of gas or water drive been intensively investigated. Most published articles have large the facts established in the labora tory to the primary production of oil from flush fields- This Paper is not based on any new observations, but is an attempt to apply some of the conclusions obtained in the laboratory and described in the literature to the recovery of oil from depleted pools by secondary methods. One of the most important factors that determine whether or not a secondary-recovery operation is economically successful is the ratio of injected fluid to oil recovered. This ratio may be expressed as the over-all or cumulative gas-oil ratio if gas is the driving medium, or water-oil ratio if water is the driving medium. Recent theoretical and experimental work has shown that the relative amounts of

Jan 1, 1944

By Parke A. Dickey, Robert B. Bossler

The presence of connate water in oil sands is of far greater practical significance in secondary oil-recovery operations than it is in primary operations. The percentage saturations of oil, water, and gas in a depleted field determine whether it will be economically possible to recover oil by secondary methods, and whether water-flooding or gas-driving, or either, will be successful. It is suggested that economic recovery of oil by secondary water-flooding can occur only when a rich bank of oil is formed by the encroachingm water. If the sand has a greater effective permeability to water than it has to oil before flooding, a bank will not be formed, and water-flooding will not be successful, although gas-driving may be. Published results of laboratory work indicate that the effective permeability of a sand to oil and water depends primarily on the saturation of the sand by these phases. They also indicate that a small difference in relative saturation produces a large difference in effective permeability to the phase in question. There thus exists a critical range of saturations, wherein a small change in oil and water content of the sands will make water-flooding possible or impossible. In gas-drive operations the water saturation is less critical but no less important. The presence of connate water in a sand increases the proportion of the residual oil that may be recovered by gas drive. Sands containing oil saturations too low and water saturations too high to make water-flooding possible can often be subjected to gas drive with economic recovery of oil. The results of laboratory work on test samples that do not contain water cannot be applied to normal field operations. More tests on cores containing water as well as oil are desirable, and the improvement of coring technique is necessary. However, sufficient data are already available to enable an operator to use core data intelligently in estimating the chances of a secondary oil-recovery program. Introduction In recent years laboratory work has led to a much better understanding of the principles of oil-reservoir performance. The general principles of the expulsion of oil from sandstone by gas or water were developed by geologists of the Second Geological Survey of Pennsylvania in the 1870lsl but only recently has the mechanism of gas or water drive been intensively investigated. Most published articles have large the facts established in the labora tory to the primary production of oil from flush fields- This Paper is not based on any new observations, but is an attempt to apply some of the conclusions obtained in the laboratory and described in the literature to the recovery of oil from depleted pools by secondary methods. One of the most important factors that determine whether or not a secondary-recovery operation is economically successful is the ratio of injected fluid to oil recovered. This ratio may be expressed as the over-all or cumulative gas-oil ratio if gas is the driving medium, or water-oil ratio if water is the driving medium. Recent theoretical and experimental work has shown that the relative amounts of

Jan 1, 1944

By M. Metzger, J. C. Bilello

Microyielding in 99.999 pct Cu occuwed in two distinct parabolic microstages and was substantially indeoendent of grain size at the relatiz~ely large grain sizes stzcdied. The strain recouered on unloading was a significant fraction of the forward strain and was initially higher in a copper-coated single crystal than in poly crystals. Results were interpreted in terms of cooperative yielding and short-range dislocation motion activated otter a range of stresses, and a formalism was given for the first microstage. It was suggested that models involving long-range dislocation motion are more appropriate for impure or alloyed fcc metals. THERE are still many unanswered questions concerning the degree and origin of the grain size dependence of plastic properties. In the microstrain region, a theory of the stress-strain curve proposed by Brown and Lukens,' based on an exhaustion hardening model in which the grain boundaries limit the amount of slip per source, accounted for the variation with grain size of microyielding in iron, zinc, and copper.' This theory assumes N dislocation sources per unit volume whose activation stress varies only with grain orientation. Dislocations pile-up against grain boundaries until the back stress deactivates the source, which leads to a relationship between the axial stress and the strain in the microstrain region given by: where G is the shear modulus, D the grain diameter, a the flow stress, and a, is the stress required to activate a source in the most favorably oriented grain.3 If this or other grain-boundary pile-up models are correct, then the reverse strain on unloading would be much larger for a polycrystalline specimen than for a single crystal. Also, the microplasticity would become insensitive to grain size if this could be made larger than the mean dislocation glide path for a single crystal in the microregion. These questions are examined in the present work on polycrys-talline copper and a single crystal coated to provide a synthetic polycrystal. EXPERIMENTAL PROCEDURE Tensile specimens 3 mm sq were prepared from 99.999 pct Cu after a sequence of rolling and vacuum annealing treatments similar to those recommended by Cook and Richards4-6 to minimize preferred orientation. Grain size variation from 0.05 to 0.38 mm was obtained by a final anneal at temperatures from 310" to 700°C. Dislocation etching7 revealed pits on those few grains within 3 deg of (111). For all grain sizes dislocation densities could be estimated as -107 cm per cu cm with no prominent subboundaries. The single crystals, of the same cross section, were grown by the Bridgman technique with axes 8 deg from [Oll] and one face 2 deg from (111). An anneal at 1050°C produced dislocation densities of 2 x 106 cm per cu cm and subboundaries -1 mm apart in these single crystals. A Pb-Sn-Ag creep resistant solder was used to mount the specimens, with a 19 mm effective gage length, into aligned sleeve grips fitted to receive the strain gages. All specimens were chemically polished and rinsed8 to remove surface films just prior to testing. The synthetic polycrystal was made by electroplating a single crystal with 1 µ of polycrystalline copper from a cyanide bath. Mechanical testing was carried out on an Instron machine using two matched LVDT tranducers to measure specimen displacement, the temperature and the measuring circuit being sufficiently stable to yield a strain sensitivity of 5 x 107. At the crosshead speeds employed, plastic strain rates were, above strains of 10¯4, about 10¯5 per sec for polycrystalline specimens and 10-4 per sec for the single crystals. Plastic strain rates were an order of magnitude lower at strains near l0- '. A few checks at strain rates tenfold higher were made for reassurance that the initial yielding of polycrystalline copper was not strongly strain-rate dependent. Test procedures followed the general framework outlined by Roberts and Brown.9,10 An alignment preload of 8 g per sq mm for polycrystals, and 2 to 4 g per sq mm for single crystals, was used for all tests. These gave no detectable permanent strain within the sensitivity of the present experiments; although at these stress levels, small permanent strains are detectable in copper with methods of higher sensitivity.11 12 stress and strain data are reported in terms of axial components. RESULTS General. The initial yielding is shown in the stress vs strain data of Fig. 1. For polycrystals, cycle lc, the loading line bent over gradually without a well-defined proportional limit, and almost all of the plastic prestrain appeared as permanent strain at the end of the cycle. The unloading curve was accurately linear over most of its length with a distinct break indicating the onset of a significant nonelastic reverse strain at the stress o u, indicated by the arrows. The yielding in subsequent cycles, Id and le, had the same general character. The single crystal behavior, shown to a different scale at the right of Fig. 1, was different in that initially the nonlinear reverse strain was unexpectedly much greater than for polycrystals. It should be noted that these soft crystals had a small elastic

Jan 1, 1970

By E. A. Ernst, N. F. Carpenter

The benefits derived from an acidizing treatment are a function of the penetration achieved by the acid before complete spending. Additional penetration may be achieved by (1) controlling acid leak-08 into formation pores in the channel faces, and (2) retarding the reaction rate of the acid. A recently developed chemical additive consists of a synthetic polymeric material which absorbs hydrochloric-acid solutions, when suspended therein, swelling up to 40 times its original volume. These swollen particles have the ability to deform and seal-08 formation pores, providing fluid-loss control. In addition, they provide a diffusion barrier between the fracture face and the acid solution, prolonging the spending time of the acid. Field applications of this new technique have shown promising results. A method of conducting acid fluid-loss tests, using carbonate cores, is believed to provide fluid-loss data that are more representative of formation conditions than the conventional filter-paper determinations. INTRODUCTION The concept of oilwell acidizing has changed since its first commercial application, 30 years ago. Originally, it was visualized that the acid penetrated thousands of tiny pores and flow channels in the matrix rock, enlarging them by dissolving the carbonate walls. The resultant permeability increase was assumed to be the responsible factor in increasing production from the well. Recent laboratory studies,' however, have shown that this does not provide the complete picture. Although this type of individual pore penetration by the acid does take place during acid "soaks", designed to overcome "skin effect" due to mud invasion in the immediate vicinity of the wellbore, many years of experience have shown that considerable pressure is required to attain any appreciable injection rate into the fine capillary pores of the rock. During most acidizing treatments, the bottom-hole pressure build-up due to the restriction of flow into the formation exceeds the "breakdown" pressure of the rock so that a fracture is induced. In most cases, such fractures open up along natural, incipient fissures and zones of weakness in the rock and, therefore, tend to follow the natural stress pattern of the rock—whether it be horizontal, vertical or inclined. Because of the comparatively greater permeability of the channel in relation to that of the matrix, the bulk of the acid volume is diverted into the newly opened fracture. Here it quickly penetrates the formation, opening and ex- tending the fracture in much the same manner as a conventional fracturing fluid. Unlike the fracturing fluid, however, most acidizing solutions contain no propping agent; thus, the open fracture will again close when the injection pressure is relieved. Laboratory studies2 have shown that in many cases the etching of the fracture faces, resulting from the reaction between the acidizing solution and the carbonate rock, is nonuniform due to the heterogeneity of the rock structure. As a result, the two fracture faces no longer match when pressure is released, and support pillars and intermediate voids remain, forming a high-conductivity channel for well fluids. Unfortunately, this is not true over the entire area of the fracture, but only over that portion of the fracture where the rock has been partially dissolved by the acid. The acid solution spends as its travels away from the wellbore; once it has completely spent, even though it may provide additional mechanical fracture extension, no additional benefit due to etching of fracture faces can be expected. Studies of acid reaction rates under formation conditions,3 observing the effect of different variables upon spending time, have shown that the reaction was often so rapid that very little penetration of the formation occurred before the acid was spent. Study was undertaken to devise methods of increasing the penetration of the acid before spending, so as to provide greater benefit from the acidizing treatment by etching a greater portion of the fracture faces. Several techniques were devised to accomplish this purpose. First, chemical additives were developed which were designed to retard the reaction rate of the acid, causing it to penetrate a greater distance from the wellbore before finally becoming spent. Another method was to increase the injection rate of the acid. However, it was found that the resultant increased shear tended to accelerate the reaction rate of the acid, partially offsetting the benefits of the higher injection rate insofar as achieving increased penetration before spending was concerned.' Another approach to the problem of achieving increased penetration was the development of fluid-loss additives for acid solutions, which would minimize the volume of acid lost into formation pores in the fracture faces and provide maximum fracture extension for the volume of acid injected during the treatment. The use of fluid-loss additives is now considered the most effective method of providing maximum fracturing-fluid efficiency.~ Unfortunately, this latter technique does not solve the problem of rapid reaction rate, with consequent limitation of the fracture area benefited by reaction with unspent acid. A newly developed acid additive overcomes many of these limitations by providing the dual benefits of fluid-loss control and mechanical retardation of acid reaction

By Nicholas J. Grant, Italo S. Servi

Extensive data of minimum creep rates and rupture times for high purity and commercial aluminum confirm the existence of a transition range from the low temperature-type to the high temperature-type behavior. The data are analyzed in line with the suggested theories of deformation of metals. CONSIDERABLY more work has been done on the rupture and creep behavior of commercial alloys than on the less complex, high purity metals. As a result, certain fundamental behaviors are overlooked. One of the lesser known variables affecting the high temperature behavior of metals is the impurity content (or alloy content). Impurities are known to affect strongly the recrystallization temperature, electrical resistivity, and other properties of metals, but the effect on creep and other high temperature mechanical properties has been determined for very few materials. In view of these facts aluminum appears to be a fairly ideal metal, since it is available in a wide range of purity contents from 99.995+ down through the 2s (99.0 + Al) and 3s (1.2 Mn) grades in small steps. It is highly resistant to oxidation and other surface instabilities, leaving recrystallization and grain growth as virtually the only instabilities. Control of grain size is also well standardized. Limited data on the creep of aluminum have been obtained by Dushman et a1.l for high purity aluminum; by Sherby2 on 2s aluminum of variable grain size; and by Dorn and Tietz³ on cold-worked 3s aluminum. Experimental Procedure The apparatus consisted of a constant stress, creep testing unit similar to the type described by Hop-kin.' The specimens were held at temperature for 30 min before loading. The loading time was less than 2 min. Factors affecting the accuracy of the data were: 1-—the temperature gradient and control, ± 3°F; 2-the stress determinations, ± 1.5 pct; and 3—elongation measurements (1 in. gage), ? 0.001 in. Three grades of aluminum were tested: 1— high purity (99.995 pct Al), 2—2s (99.3 pct Al), and 3—3s (98.2 pct Al). The spectrographic analyses of these materials are reported in Table I. The specimens were annealed then electropolished in a perchloric-acetic mixture before testing. Data on heat treatments and grain size obtained appear in Table 11. The entire creep curve was determined for almost all of the tests. A few tests were interrupted after the beginning of the third stage of creep, and in these cases the rupture time was estimated. Experimental Results Constant stress creep-rupture testing gives a much longer, more accurately measurable second stage of creep than constant load testing. This behavior is in agreement with the results obtained by Andrade for lead (see Fig. 1). If the test is run to completion, the third stage of creep appears as soon as stress intensification occurs. In the case of specimens which fail in a ductile manner, the stress intensification begins when the sample starts "necking". This differs from the "high temperature brittle" specimens in which the stress intensification is caused by intercrystalline cracking. These specimens

Jan 1, 1952

By J. B. Conway

Stress-vuptuve data for several of- the refractory metals are frequently found to yield a linear relationship between the Larson-Miller parameter and the logarithm of the applied stress. In such cases linear stress-rupture isotherms result with slopes bearing a definite relationship to the temperature. It also follows that the stress to produce rupture in a certain period of time will be linear in temperature. Data for several refractory metals have been reviewed and excellent linearity is shown in this type of isochronal plot. In addition, the af ore - mentioned lineavity leads to a linear relation between the log of the stress to produce rupture in a certain time and the homologous temperature. This has been illustrated for the Group VI-A metals, tungsten and molybdenum. EXTENSIVE use has been made of the Larson-Miller' parameter in the interpolation and extrapolation of stress-rupture and creep data. In those cases where this particular parametric approach is applicable a convenient and fairly straightforward procedure is made available for the correlation of experimental stress-rupture data. It is quite common to employ this parameter in the form of a master rupture plot in which the parameter, T(C + log tr), is expressed as a function of log stress. In many cases this functional relationship in log stress is linear within acceptable accuracy and hence the following relation results: where P is the parameter, C is the Larson-Miller constant, T is the absolute temperature, t~ is the rupture time, a is the stress, and a and b are constants. Examples of such a relationship are contained in the work of Green, Smith, and 01son2 dealing with high-temperature rupture behavior of molybdenum and in the work of Green' dealing with the high-temperature behavior of tungsten. In addition, pugh4 has shown a similar linearity for some fairly low-temperature data for molybdenum. It can be shown that when the relationship in Eq. [I] is exhibited certain generalizations can be made concerning the form of the stress-rupture isotherms. For example, rearranging yields: For a given material (constant C) at a given temperature the first term on the right-hand side of Eq. [2] is a constant and hence this equation defines a straight line when log stress is plotted as a function of log-rupture time. This is recognized as the standard form usually employed in this type of data presentation. Such linearity then suggests the linear form of the Larson-Miller parameter. Or, in other words, the linear parametric relationship in Eq. [2] results only when the stress-rupture data are linear on a log-log plot of stress vs rupture time. Another interesting observation can be made in regard to Eq. [2]. It can be noted that the slope of the stress-rupture isotherms is given by - T/b and hence a direct calculation of the constant b is available. It also follows that since the value of b is the same for all temperatures the slopes of the various isotherms on the log-log stress-rupture plot cannot be the same. Indeed, the existence of the relationship in Eq. [2] precludes a system of parallel lines on this common stress-rupture plot. As a matter of fact it further specifies that in addition to being nonparallel the slope of these isotherms must decrease (i.e., become more negative) with increasing temperature. Such a condition is indeed found to exist in the case of the stress-rupture data reported for molybdenum.' As a corollary to the above, it may be stated that stress-rupture data which do not lead to a linear log-log stress-rupture plot or whose isotherms do not exhibit a decrease in slope as the temperature increases will not yield the linear relationship of Eq. [I]. Applying Eq. [2] to two different temperatures and solving for C yields: Eq. [3] affords a simple and rapid method for calculating the Larson-Miller constant from the log-log stress-rupture plot. The slope of a given linear isotherm is measured and the value of "b" calculated based on Eq. [2] as: slope = - -Tb Then at an abscissa value of 1.0 hr (making log tr in Eq. [3] equal to zero) read the stress corresponding to rupture for two different temperatures. Substitution in [3] yields: A value of the Larson-Miller constant can thus be calculated from a few simple mathematical procedures employing data read directly from the log-log plot of the stress-rupture data. Of course, it is not to be overlooked that the above reasoning has been based on the linear relationship of Eq. [I] being applicable. However, if as mentioned above the log-log plot is

Jan 1, 1967

By C.H. Davis, W.H. Bassett

The ease and value of the application of spectrum analysis to industrial chemistry appears to be appreciated in few of the large works laboratories of this country. For 8 years, this analysis has been of great value to the authors in both analytical and metallurgical work. To the analyst the complete qualitative analysis of an unknown alloy, revealed by a spectrogram, is a sure basis for the planning of the most direct and rapid method of attack. As the determination of each element proceeds, the purity of precipitates may be checked as often as desired. The spectrograph proves invaluable in the recognition of impurities, the separation of which would entail a lengthy and difficult procedure, or when the weight of an unknown is less than is necessary to complete the desired determinations. A few hundredths of a gram will usually suffice for spectrographic analysis. In the separation of the rarer elements, the spectrograph will show, with precision, the point where each step has been successful. In zinc of certain classes, indium, gallium, and germanium have been isolated in this way; the presence of antimony in lake coppers has been proved; and bismuth has been detected in zinc and in alloys where the presence of a few thousandths of a per cent. would be harmful. An antimony precipitate in a delicate determination may contain a considerable proportion of tin or arsenic, both of which will be revealed. The spectrograph is consequently important to the metallurgist as well as to the analyst. Impurities in raw material are often a source of annoyance, especially when their detection involves delay and costly analytical work. Whethcr low conductivity in copper is due to arsenic, nickel, or something else may be cluickly found out. Residual traces of boron, magnesium, manganese, silicon, vanadium, and other deoxidizing agents are easily identified where wet analysis may fail to reveal their presence, even after days of effort. Complex alloys of any kind are dissociated by the spectro-

Jan 1, 1923

By W. H. Bassett, C. H. Davis

The ease and value of the application of spectrum analysis to industrial chemistry appears to be appreciated in few of the large works laboratories of this country. For 8 years, this analysis has been of great value to the authors in both analytical and metallurgical work. To the analyst the complete qualitative analysis of an unknown alloy, revealed by a spectrogram, is a sure basis for the planning of the most direct and rapid method of attack. As the determination of each element proceeds, the purity of precipitates may be checked as often as desired. The spectrograph proves invaluable in the recognition of impurities, the separation of which would entail a lengthy and difficult procedure, or when the weight of an unknown is less than is necessary to complete the desired determinations. A few hundredths of a gram will usually suffice for spectrographic analysis. In the separation of the rarer elements, the spectrograph will show, with precision, the point where each step has been successful. In zinc of certain classes, indium, gallium, and germanium have been isolated in this way; the presence of antimony in lake coppers has been proved; and bismuth has been detected in zinc and in alloys where the presence of a few thousandths of a per cent. would be harmful. An antimony precipitate in a delicate determination may contain a considerable proportion of tin or arsenic, both of which will be revealed. The spectrograph is consequently important to the metallurgist as well as to the analyst. Impurities in raw material are often a source of annoyance, especially when their detection involves delay and costly analytical work. Whethcr low conductivity in copper is due to arsenic, nickel, or something else may be cluickly found out. Residual traces of boron, magnesium, manganese, silicon, vanadium, and other deoxidizing agents are easily identified where wet analysis may fail to reveal their presence, even after days of effort. Complex alloys of any kind are dissociated by the spectro-

Jan 1, 1923

It is particularly interesting at this time to notice the recommendations of F. L. Bishop, clean of the University of Pittsburgh School of Engineering as to the types of engineers required and the training that should be given each type. Dr. Bishop's recommendations, which follow, are substantially the same as the first two recommendations made by resolution at the National Conference recently held to discuss commercial engineering problems. This provided business training for the engineer arid engineering training for commercial enterprises. Dr. Bishop says: "The first type is that of the man who may be called a technician, who is highly trained in science and mathematics, who possess the instinct of the research man and who can devote his entire time to highly technical research problems, either in the research laboratories which are now rapidly being developed in the large industries, or by applying the results of his research to engineering science. For the training of this type of man, there is needed the best of scientific equipment, the members of the faculty must be those who are intimately interested in research problems, and the student himself must have what is sometimes called a mathematical mind. It is doubtful if this type of nan can be developed in a four-year course under existing conditions. In fact, it is probable that such a man can be developed only M. a school which has a thorough graduate department. "The second type which seems to be demanded by the industries is the man who has a broad general knowledge of engineering subjects and can apply that knowledge in an effective way in present engineering problems. He must have ability to command men, a knowledge of the applications of economic principles to industries, and a broad training in the so-called humanities, since he is the man in contact with men of other types in other fields of human activities. He should not be a research man, his training in mathematics need not be of necessity so extensive as that of the research technician, but his understanding of engineering problems should be extensive. Such a man cannot be trained in the ordinary schools because of the artificial conditions which of necessity exist in academic institutions. He must become familiar with the industries while yet, a student in order that he may understand thoroughly the application of his theoretical courses in school and their application to industries, and also that he may become familiar in the formative period of life with the problems of labor and the human factor in engineering. It is in the development of this type of man, who is to become. the manager and operating head of our large manufacturing industries, that the advantages to be derived from the cooperative system of engineering education are needed."

Jan 9, 1919

By C. F. Cornell, R. C. Emmett, D. A. Dahlstrom

FOR many years the disk-type and cloth-covered drum filters have found widest application in liquid-solids separation, which uses continuous filters. The disk type is less expensive, occupies less floor space per square foot of filtration area, and re- quires negligible down time for filter media changing. However, because filter cloth is billowed out by the blowback in the cake discharge, it is very short-lived if the scraper blades are set too close. Consequently cake weight is very important in assisting cake discharge, which normally necessitates a minimum cake thickness of 3/8 to ½ in. Also, the vertical position of the disks eliminates the possibility of efficient cake washing for removal of soluble values. The disk-type filter is generally limited, therefore, to applications that require no cake washing and form relatively thick cakes within the normal range of filter cycle times. The conventional cloth-covered drum filter is a more flexible unit, permitting wider variation in the percentage of cycle time devoted to cake formation, dewatering, or washing, as required by the application. Thinner filter cakes can be discharged be- cause a horizontal line across the filter medium at the location of the scraper blade is equidistant from the edge of the blade at all points. The scraper blade therefore may be set a short distance from the filter medium or, where wire winding is not used, a floating scraper can be utilized so that the contour of the cloth can be followed. The drum filter is generally employed when there are difficult filtering slurries with resultant thin cakes or when cake washing to recover soluble values must be practiced.

Jan 2, 1958

By C. E. Taylor, L. V. Fegan

With on-stream electrical-resistance measurement as a basis, Bethlehem Steel developed a system for the completely automatic control of moisture in the feed to pelletizing. This system was later successfully adapted to the sintering process, with automatic control of moisture serving to maintain the air permeability required for effective burnthrough. Control of moisture content is an important factor in the agglomeration processes by which iron ores are converted into either pellets or sinter for use in blast furnace burdens. In both pelletizing and sintering the iron ore feed must be mixed with the proper amount of water so that capillary attraction and surface tension forces can be utilized to cause the ore particles to coalesce and form larger agglomerates. The success or failure of the entire pelletizing or sintering process depends on maintaining the proper moisture. Therefore, continuous automatic control of moisture is one of the conditions for the automation and optimum use of both pelletizing and sintering processes. In pelletizing, variation in moisture can cause ball size to change and is a common cause of cycling which results in a fluctuating feed to induration. Excessive moisture can cause lumps to form at the cutter bar and contributes to the formation of buildup on the green pellet screens. Green pellets with excess moisture deform and reduce bed permeability. In sintering, accurate control of moisture is also important because moisture must be within the limits that give the bed the required permeability for good burnthrough. In response to these problems, a moisture meter, based on the principle of electrical resistance measurement, was developed. This moisture meter has been a key factor in the development of systems for providing uniform feed of concentrates in most of Bethlehem's pelletizing and sintering plants. The automatic moisture control system for pelletizing was successfully plant-tested and resulted in the following: (1) Control of moisture in the green pellets to +0.2%. (2) Up to 50% reduction of bentonite consumption. (3) Control of unscreened green pellets so that 85% of the furnace product at Cornwall was within the size range of -5/8 +3/8 in. (4) Improved quality of product with a tumble test of 94 and a "Q" index of 90 as the result of feeding a consistently uniform feed to a shaft furnace. In sintering, where sinter-mix temperature change and variable feed could cause errors in moisture measurement, the system was designed to maintain the correct moisture under virtually all plant operating conditions. It was successfully plant-tested and is now in use in most of Bethlehem's sintering plants. The system achieves: (1) Control of moisture within the desired limits for optimum production. (2) Continuous measurement and control of moisture even with intermittent feeding of mix, so that attention by the operator is seldom required. The two automatic control systems provide smoother startup, minimize upsets and contribute to the consistent control of process variables in pelletizing and sintering. MOISTURE-CONTROL SYSTEM FOR PELLETIZING Fig. 1 shows the general arrangement of the system for automatic control of moisture in pelletizing.1 In this system a bin level controller, using a single probe which regulates filter speed, maintains a uniform low concentrate level in the bin.' The moisture meter, comprised of an analyzer and control components, continuously measures the moisture in the bed and adds water to adjust to the desired level. The meter is placed in an open-loop (feed-forward) control, i.e., water addition occurs downstream from the probes. Filter vacuum must be set so as to produce a filtercake moisture which is below the optimum for pelletizing. Bentonite is added after the

Jan 1, 1969

By J. Szekely, V. Stanek

Steady state heat transfer and fluid flow rates are predicted for the counter-current contacting of gas and solid streams. For a .fixed pressure drop across the bed the convective heat transfer rate is affected by the gas flow rate, which in turn is affected by the temperature distribution in the system. Variations in bed voidage and in particle size were found to change the predicted temperature profiles quite markedly, in particular when the thermal capacities of the gas and solid streams were equal. IN Part I we examined the effect of step and pulse changes in the inlet gas temperature on transients in the flow of gases through fixed packed beds. Here we shall discuss heat flow and fluid flow interactions in the counter-current heat exchange between packed solids and a gas stream. Counter-current heat exchange in packed beds has been extensively studied. In his now classical paper, Furnas' assumed constant property values and developed a simple analytical. expression for the temperature profiles in the gas and in the solid stream. A highly sophisticated analysis of counterflow systems, allowing for transients and interparticle conduction was developed by Amundsen. In preparing a very readable review of this topic Elliott' also presented a number of elegant solutions, including the case involving heat generation. A great deal of work has been done on the application of these concepts to the modelling of the blast furnace. However, in all this previous work the mass flow of the gas was regarded as a quantity independent of the gas-solid heat exchange process. In the following we shall consider counter-current heat exchange between a gas stream and a packed bed of solids, under conditions where the pressure drop across the bed is specified, rather than the mass flow of the gas. FORMULATION Consider a packed bed, extending from y' = 0 to y' = L, in which moving solids and a moving gas are contacted in a counterflow arrangement. Let cold solids, with an initial temperature Tsi and mass flow GA, enter at y' = L, and hot gas with an initial temperature of Tgi and mass flow Gg enter at y' = 0. In contrast to the problems considered in Part I this system has a nontrivial steady state and we shall restrict our attention to the study of the pressure drop flow relationships and the resultant temperature distributions for steady state conditions. Under these conditions the formulation of the problem requires the statement of the following: 1) heat balance on the gas 2) heat balance on the solids 3) the mechanical energy balance equation and in addition the knowledge of the equation of state, and a functional relationship between viscosity and temperature and an expression for the heat transfer coefficient in terms of the other parameters. On neglecting temperature gradients within the solids and for a constant mass flow of the gas, the solution to this problem is well known.'" The expressions for the temperature profiles of the gas and solid streams may be put in the following form: where Tg and T, denote the dimensionless gas and solid temperatures respectively, y is a dimensionless distance, and R is the ratio of the thermal masses. These quantities are defined as follows: For the particular case of equal thermal mass capacities by the gas and the solid, that is R = 1, the Eqs. [1]and[2] simplify to Eqs. (71 and[8], respectively: i.e., the resultant profiles are linear. As for most practical cases , solutions given by Eqs. [7] and [8] will contain only the inlet temperatures as parameters. For a fixed, predetermined value of C;b the above

Jan 1, 1970

By P. E. Hildebrand, S. W. Mao, C. N. Crain

Hydrologic and economic criteria figure in many obvious ways in water resources development, but they are rarely linked quantitatively, and most of the applications are pertinent only to the case in point. In the preparation of a regional plan for the massive program of groundwater development in the Punjab, situations have arisen where the choice among two or more alternatives was made by analyzing the economic implications of critical hydrologic parameters. Two of these situations which are of more or less general interest are described herein. The first involves basic development policy, i.e., the question of whether groundwater development should be based on the demand of the economy, or the conservation concept of safe yield. The analysis demonstrated that mining of groundwater is clearly indicated for areas where alternative supplies are unavailable. The second problem involves integrating hydrologic data into an economic model to determine optimum well design. From an analysis of all pertinent factors, a simple nomograph was derived for determining well specifications on site during construction. The nomograph can be modified for use in any alluvial terrain. In the Northern Zone of the Indus Plains —the region known as the Punjab- Pakistan is proceeding with integrated development of water and land resources on a scale never before contemplated. The heart of the development plan is a massive program of groundwater development to supplement canal irrigation supplies and to provide drainage relief to the irrigated lands. By the close of 1966 about 2500 high-capacity wells were in operation and furnishing the water supply and drainage requirements for nearly two million irrigated acres. The development plan calls for the construction of a total of nearly 30,000 wells with an aggregate capacity of 120,000 cfs by 1980. This is part of an integrated program eventually affecting over 20 million acres of irrigated lands. [This development program is administered by the West Pakistan Water and Power Development Authority (WAPDA) for which the firm of Tipton and Kalm-bach, Inc. serves as regional planning consultant for the Northern Zone. The material presented herein is derived from planning studies which have been made in connection with the preparation of a regional development plan for the Northern zone.] Pakistan is proceeding with this large-scale development of land and water resources at a time when she is at the threshold of an almost calamitous population growth. Furthermore, she is attempting this development at a time when most of her usable land is already occupied and her food demands exceed current production. Here in the Northern Zone is one of the largest continuous areas of irrigated land in the world, easily irrigated, with a warm, dry climate and ample potential supplies of surface water and groundwater. Except for an abundance of land and labor, other primary resources are lacking or in very limited supply. The agriculture sector so dominates the economy that only by means of an effective development of the agricultural resources can other sectors grow and contribute to a viable economy. Because of inadequate irrigation, farming here has not effectively participated in the twentieth century revolution in agriculture, and only by means of massive development of potential supplies can Pakistan catch up. Capital for any kind of mass development must come from the outside. But the overriding restraint to development of the land and labor resources is the availability of water. ECONOMICS OF DEVELOPMENT The decision-making process in planning regional development becomes increasingly complex as the various sectors of the economy become more highly developed. Where, as in this case, one sector dominates the economy and its development can be considered the key to development of other sectors, the decision-making process is simplified and it is easier to identify alternatives and to trace the prob-

Jan 1, 1970

By H. H. Smith, G. J. Danek, M. R. Achter

Nickel, Type 316 stainless steel, and copper show decreases in reversed bending fatigue strength with increases in air and oxygen pressure. The leveling off of the log N us log p curve for nickel at 300" and 816°C is discussed in terms of a model in which surface saturation gives rise to a critical pressure. A metallographic study indicated that the effect of environment on crack initiation and growth rates is a function of temperature. It is shown that small amounts of impurities in inert gases may substantially reduce the fatigue strength of nickel. 1n a previous investigation1 of high-temperature bending fatigue in air and in vacuum, reversals in the effect of environment with changes in test conditions were atrributed to a mechanism consisting of two processes acting in competition. One of them, oxidation strengthening, has been demonstrated in a straightforward manner by measuring the rupture strength of a sintered nickel-oxide bond.' The detailed operation of the other process, facilitation of crack propagation by surface absorption of oxygen, is uncertain. Thompson et UZ advanced the possibility that the formation of an oxide layer prevented rewelding of cracks during the compressive part of the cycle, while Wads worth and Hutchings4 further proposed that the reaction of oxygen with atoms at the tip of the crack helped the metal to break there, a possibility which has also been advanced to explain crack formation in creep.5 A difficulty in arriving at a mechanism for this lowering of fatigue strength in air is the inconsistency of some of the data. For example, Wadsworth and Hutchings4 found an approximately linear decrease of log cycles-to-fracture (N) with an increase of log pressure-of-air (p) for copper and aluminum at room temperature, while snowden,' although finding a similar linear dependence for aluminum, observed a stepped curve for lead. Between l0-' and 10"1 torr there is a sharp decrease in the fatigue life of lead with increasing air pressure, but plateaus, signifying no dependence on pressure, are found at higher and lower pressures. If, as discussed elsewhere: these environmental effects arise from the adsorption of gas on crack surfaces, it would be expected that as the pressure is increased a saturation point would be observed, beyond which there is no further effect. To gain further information about the form of the log N vs logp curve, it was decided in the present investigation to repeat this type of measurement at elevated temperature on nickel, copper, and Type 316 stainless steel. An additional object of this program was

Jan 1, 1963

By R. S. Shoemaker, F. W. McQuiston

REFINERY SECURITY "Highgrading, " a polite word for stealing gold and silver, has been a way of life since the metals in native form have been mined or produced. Unfortunately, in the past, highgraders were not always severely prosecuted or even looked upon unfavorably in their communities. Recent high metal prices with attendent world wide publicity, however, has made highgrading or thievery again a serious problem in mines and plants. When a small button of gold the size of the end of ones little finger has a value equal to about one week's wages, the safe-guarding of gold production by enforcing tight security measures becomes a prime responsibility of management. The higher the gold price, coupled with unrestricted owner- ship, the greater the temptation to “get-your-cut”, and diligence by management must become an integral part of plant security. Primary security begins by knowing the expected gold production and the sampling of a gold ore mill feed for this determination has proved not reliable. However, solution flows can be accurately sampled and measured thereby closely predicting the gold recovered each day as precipitate. The progressive record of total ounces of gold contained in the precipitation press, referred to in cyanidation plants as I1solution calll1 predicts the accumulated production. The "callH is an important adjunct to security and extreme caution must be used so that the pregnant solution meter and sample are confined in a security area. It should be recognized that this key sample may be the target for Ifdoctoring" by trusted insiders (assay office employees) as a preliminary step for stealing precipitates and/or metal. Security measures similar to the following were adopted after one operation experienced a sizeable theft of gold precipitate and metal by trusted employees. The refinery area where precipitates are handled and melted to bullion and all other gold products are kept should be completely enclosed with a tight security fence preferably of solid construction. Access to this enclosure should be through one of two electrically controlled gates, one for personnel and another for occasional truck entrance. Admittance should be restricted to essential personnel who are required to sign a register in and out with the date and time. I£ there is a "back gate" to the restricted fenced area, it should remain locked except in an emergency and then opened only by a supervisor. Television monitoring cameras viewing the gate entrance and other sensitive areas connected to a viewing screen located in the general office afford visual observation at all times.

Jan 1, 1975

By John Randall

IT is a fair assumption that the main purpose of any diagram is to present facts to the eye in more convenient form than they could be tabulated in figures, and this implies that a screen diagram should set forth in a convenient and familiar form certain facts as to the character of the material screened regardless. of the screen standards used, and it seems particularly desirable on account of the well-known differences in the size of openings of different laboratory screens having the same nominal mesh. In making screen-sizing tests it has been customary to first consider the largest size, going progressively to the smallest, and this seems to have led to the practice of placing the smallest size at the right-hand side of the diagram and .measuring toward the left. This is not altogether convenient and might he changed to advantage, but for illustration I have preserved that feature and present the method just as I have used it for over 2 years. Direct plotting in which the intervals on the diagram are proportional to the sizes of the openings, or to the arithmetical difference between them, seems at first sight more natural and is extremely useful for certain purposes, but it makes the diagram very crowded in the smaller screen sizes while the larger ones occupy unnecessary space, snaking it less convenient for most purposes, and for that reason the method here discussed is the well-known one based oil the ratio between openings, and is plotted in logarithms instead of the direct values of the screen opening. Metric coordinate paper is convenient, although .not necessary; it is recommended, as the use of the metric scale gives a diagram of convenient size, but any scale of equal. parts may be used. In order to make any screen diagram translatable in terms of any standard screen size, it is necessary to have rioted on the size scale of the diagram all points corresponding to the openings of the various screens in question, instead of a single series 'of points as with a single screen. In drawing the diagram assume 0.001 in. (corresponding approximately to 0.025 mm.) to be the smallest size to be considered and fix this as the zero point at the lower right-hand corner of the diagram. This value is selected because the values are to be plotted in logarithms, and the logarithm of 1 is zero. Then lay off to the left for the position of each screen

Jan 9, 1917

By J. K. Stanley

Iron-cobalt alloys in the range of 35-50 pct cobalt are of interest in the electrical industry because they possess the highest magnetic saturation of any magnetic material known. l1,2The magnetic saturation induction of the 35 pct alloy is 24,200 gausses, compared to 21,600 for pure iron (Fig I). This difference is significant in electrical apparatus, whcre weight or space is at a premium. Saturation values higher than that for iron can be attained up to about 70 pct CO hut economics restrict the use to as low a cobalt content as possible without sacrifice of saturation. Fig 2 shows the iron-cobalt equilibrium diagram. Up to the present time, two factors have retarded the use of iron-cobalt alloys in the electrical industry for magnetic purposes.? One is the high cost of cobalt ($I.50 per pound) and the other ig the inherent brittleness of the binary iron-cobalt alloys. Straight iron-cobalt alloys up to 25 pct cobalt are ductile and easy to process to thin sheet or strip by conventional methods of hot and cold rolling, but the alloys containing higher percentages of cobalt, including those for which the saturation magnetization is a maximum (35 to 40 pct), are increasingly brittle with increasing cobalt, at least up to 50 pct, and are consequently difficult to process, either hot or cold. Work by White and Rah13 indicated that iron-cobalt alloys could be made ductile by alloying with vanadium, and after quenching the alloys (vanadium up to about 4 pct) were found to he colt1 rollable to very thin gauges. With this as a background, we resumed our work on these alloys with the objective of developing methods for economical commercial production of wide strip. For this purpose we have concentrated on the 35 pct alloy in order to obtain the highest possible saturation value. Experiments were carried out on many alloy additions to the iron-cobalt alloys and on the response of these compositions to heat treatments. This work finally culminated in a commercially producible iron-cobalt alloy which has been named Hiperco.* Materials StudIEd and Procedur' Binary alloys of iron and cobalt in the range of 35 pct cobalt are difficult to hot work (by forging or rolling) without such additions as C, Mn, Si, V, Cr, Mo, W Or perhaps others. Another beneficial effect of such additions is that they increase to a greater or less extent the strangely low electrical resistivity of these alloys about 10 microohms per cm3

Jan 1, 1948