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By Geo. H. Ashley

The following paper is intended to be suggestive only, and to open the way for discussion and further observation. Its preparation was requested only two days before the time limit set for the submission of the papers comprising this symposium. Thus no time existed for detailed studies, so it is largely a memorandum of such facts as have come incidentally to the notice of the writer in the study of coal in the field. The field study of sulfur in coal has received very little special attention or description from coal student's. The presence of sulfur concretions is noted in hundreds of descriptions, and certain benches of a coal bed may be described as "sulfury" or the presence and position of sulfur bands may be noted in coal sections in connection with sampling. It may be accepted that some sulfur is present in all coal. The amount varies greatly in different regions, in different beds, and in the same bed in different areas. The anthracite of Rhode Island comes the nearest of any coal known to the writer of being free from sulfur, several analyses of that coal showing less than 0.1 per cent. Subbitumi-nous coals in Colorado in a few places have close to 0.2 per cent. of sulfur on the dry-coal basis and in other states subbituminous coals approach this lower limit. Bituminous coals seldom run under 0.4 per cent. of sulfur on the dry basis, though in a few places dry bituminous coals in Colorado and Washington have between 0.3 and 0.4 per cent. The better known bituminous coals have almost everywhere over 0.4 per cent. The best of the Pocahontas and New River coals run close to 0.4 per cent., but there is very little commercial coal in Pennsylvania, Ohio, Indiana, Illinois, Kentucky, or the other states, that runs under 0.5 per cent. on the dry basis. From these minimum figures, the amount will range up to 5 or 6 per cent. or higher if visible sulfur is not excluded. It must be remembered that the usual analysis of a coal bed is not intended to give the total proportion of sulfur in the bed but the amount in the coal after the removal of the more obvious and larger sulfur masses. Professor Parr has already pointed out that, chemically, sulfur occurs in several forms: as pyrite, organic sulfur, sulfates, and possibly as un-combined sulfur. Sulfur in the form of sulfates is commonly the obvious result of the weathering of pyrite and may be found in the coal within .

Jan 1, 1920

By C. L. Meyers, A. V. Levy, G. Y. Onoda, R. J. Kotfila

This paper presents the hypothesis that solid-solution hardening of regions in the order of tens of angstroms thick along grain boundaries is the most important mechanism controlling the ductile -brittle transition behavior of poly crystalline bcc refractory metals. Further, a physical model is developed and a general equation is derived to describe the dependence of the solute concentration at grain boundaries on temperature, nominal impurity concentration, thermal treatments, vain size, and prior plastic deformation. Analytical curves of the solute concentration at grain boundaries us temperature, calculated by means of the derived equation, are found to have the same general form as curves of ductility us temperature plotted from experimental data. Senziquantitative relationships between the transition temperature and metallurgical variables can he determined by using the physical model. The room-temperature brittleness of the poly-crystalline refractory metals (tungsten, molybdenum, and chromium) is a result of their high ductile-brittle transition temperatures. Recently studies on single crystals have revealed that, when sufficiently pure, these crystals have much lower transition temperatures than polycrystalline specimens of similar purity.'-3 For example, the transition temperature (measured by reduction in area in tensile tests) for very high-purity tungsten crystals has been reported to be as low as -50°F whereas polycrystalline specimens of similar purity had a transition temperature near 400" ~.' These results suggest that the ductile-brittle transition behavior of these polycrystalline metals can be attributed principally to the influence of grain boundaries on plastic flow and fracture. This paper contains a discussion of the manner in which grain boundaries influence the ductility of the poly-.crystalline bcc refractory metals and proposes that the segregation of impurities to grain boundaries is the most important mechanism for controlling the ductile-brittle transition behavior of these metals. Further, this paper contains an analysis of the effect of the compositional and structural variables on the grain boundary-ductility relationship, and introduces a semiquantitative model that can provide a foundation for more theoretical treatment to describe the influence of these variables on ductile-brittle transition behavior. PHYSICAL MODEL FOR PREDICTING DUCTILE-BRITTLE TRANSITION BEHAVIOR Grain Boundary Segregation of Impurities. Based on their own observations and on theoretical grounds, numerous investigators have suggested that impurities segregate to the grain boundaries. Such segregation would be expected because regions exist where both large and small foreign atoms fit with less strain than within the undistorted crystal structure. Therefore, the concentration of impurities should be higher at boundaries than within the grain body. TO estimate the degree (i.e., the ratio of grain boundary to nominal bulk concentration) to which an interstitial solute tends to segregate at boundaries within a solvent metal, the solubility rather than the size misfit could be used as a guide because solubility expresses the joint effect of both elastic and electronic factors.5 The solubilities of interstitial elements such as carbon, hydrogen, nitrogen, and oxygen are low in the group V-A metals and very low in the group VI-A metals.6 These low solubilities suggest that segregation to grain boundaries should occur for each of these solutes in both refractory metal groups. The difference between the ductility of single-crystal and polycrystalline bcc refractory metals can be described in terms of two distinct effects.4 The first of these is the general observation that grain boundaries hinder slip within grains and slip transfer between grains, and the second is that deformation is more complex in each grain of a polycrystalline specimen than it is in a single crystal. Mc Lean has pointed out, furthermore, that strong slip-hindrance effects at grain boundaries should occur in metals having strong segregation of impurities to grain boundaries. Therefore, the effect of grain boundaries on the hindrance of slip is expected to be the dominating influence on the ductile-brittle transition behavior of these polycrystalline refractory metals. cahn5 has suggested that temperature and solute mobility should influence solute equilibrium segregation at grain boundaries, and Fig. 1 illustrates

Jan 1, 1965

By B. L. Averbach

Recovery and primary recrystalliza-tion in cold worked metals are usually considered as two competing processes. Some of the effects which usually accompany recovery are: alleviation of stress corrosion tendencies, changes in thermal emf,1 damping capacity,2 electrical resistivity,2 and magnetic properties,3 and only minor changes in hardness or the related strength properties. During primary recrystalliza-tion new unstrained grains are formed at the expense of the strained matrix. These new grains eventually become visible metallographically, and nucle-ation and growth kinetics have been indicated for this process.4,5 Frequent attempts have been made to study the cold-working phenomenon by observations on the line broadening by X ray diffraction patterns. Relatively few measurements of line intensities have been made, although Brind-ley and his collaborators, 6,7,8 by means of film techniques, compared the intensities of cold worked Cu, Ni, and Rh patterns with those from chemically precipitated powders. These precipitated powders were presumed to be strain free, and it was found that the intensities for the cold-worked materials progressively decreased as the Bragg angle increased except for the first line, where there was an increase due to reduction in extinction. This was interpreted as a randomness in atomic position induced by cold work. Such randomness is similar to that caused by thermal agitation and has been described as "frozen heat" displacement of 0.08-0.10 A from the mean atomic position. In a recent study9 on the effect of cold work in metals on their powder pattern intensities, the changes in integrated intensity for heavily cold worked alpha brass were observed as a function of the annealing temperature. These measurements were made with a manually operated Geiger-counter spectrometer using CuKa radiation monochromated with a rock salt crystal. Intensity measurements were made with a scaling meter over small intervals of angle, and the equipment was so arranged that the diffracted and incident beams made equal angles with the specimen. Intensities could be compared directly by simply interchanging specimens, and comparisons from day to day were made with a standard whose line intensities did not change on aging. It was shown that a cold worked alpha brass standard was stable for at least a year. Table 1 indicates the results of the integrated intensity measurements on a 70 Cu-30 Zn brass. In the sample preparation, a brass plate was first cold rolled 50 pct and then filed, screened to —325 mesh, compacted into briquettes at a pressure of 60,000 psi and finally annealed for one hour at various temperatures up to 400°C. The briquetting pressure did not seem to influence the integrated intensities, and most of the cold work was introduced by the filing. Although this method of cold work is not quantitative, it was used to obtain random orientation (and thus uniform diffraction lines) in order to make accurate measurements of integrated intensity. Back reflection patterns were taken in each case to check the uniformity of the lines, and from the observed line broadening it was apparent that this type of plastic deformation was quite severe. Care was taken to traverse the entire background of the pattern and to assign to each peak the total intensity above this background. The bases of the diffraction lines were quite broad and spread out over several degrees, even for the narrow peaks. The theoretical intensities were calculated to include a temperature correction, a dispersion correction, and a Lorenz- polarization factor corrected for the crystal monochromated beam. In Table 1 it was necessary to match the calculated and observed values at only one point, and the rest of the experimental values were converted directly to this arbitrary scale. The integrated intensities in Table 1 are listed in arbitrary units, and the accuracy was sufficient to reproduce any of the measured line intensities to within + 1.5 units. It is evident that the percentage error on the strongest line (111) was quite low. The calculated values and the observed intensities for the cold worked material matched reasonably well. As the annealing temperature was raised, however, the intensity of the strongest reflections, particularly the (lll), decreased measurably. Since the background intensities of all of these patterns were identical, such behavior could be interpreted as a primary

Jan 1, 1950

By Jay R. Burns

Two magnesium sand-casting alloys are commonly favored in the United States. These are referred to as H and C alloys (Dow Chemical Co.) or AM265 and AM260 alloys (American Magnesium Corporation). Both are of an aluminum-zinc-manganese type. H alloy contains 6 per cent aluminum and 3 per cent zinc and is characterized by relatively good toughness. C alloy contains g per cent aluminum and 2 per cent zinc and is employed where high yield strength and pressure tightness are required. Examination of magnesium castings poured in Europe and England,1,2 however, demonstrates that H and C alloys are replaced by A8 and AZ91, respectively. That is, A8 represents a magnesium alloy having superior toughness while AZ91 is suitable for high yield strength and pressure-tight applications. The basic difference between the American and European alloys is that the foreign alloys employ a somewhat higher aluminum content and less zinc than is found in H and C alloys. The mechanical properties of the alloys, when divided into high and low-aluminum groups, are quite similar, as determined from separately cast foundry-control type test bars.3 In this paper the decrease of mechanical properties caused by any given amount of microporosity is measured for H, C, A8, and AZ91 alloys. The relative susceptibility of each of the four alloys to microporosity is also determined. Typical mechanical properties and nominal chemical analyses are reported in Table I. [ ] The apparent similarities between the two alloys in each group have led to considerable discussion as to the relative merits of each of the compositions.2 Popular points for comparison between the alloys have been the relative susceptibility of each of the four alloys to microporosity5 and the effect of this microporosity on their mechanical properties. It is primarily intended, in this paper, to show the

Jan 1, 1946

By R. D. Pehlke, J. V. Gluck

A study was made of' the effects of up to five additional solutes on the thermodynamic activity of zinc in dilute solution with molten bismuth in the range 450" to 650°C. The experimental measurements were made in a multielectrode galvanic cell apparatus employing fused LiCl-KCl as the electrolyte. The solute additions included indium, lead, tin, cadmium, copper, silver, antimony, or gold. A range of positice and negative interactiotls with zinc was covered. The experinzer~tal observations were cowlpared with the activity coefficients calculated usitlg either Wagner's first-order Taylor series rnodel or a proposed second-order solution itrteraction model. hi general, the truncated first-order Taylor series proposed by Wagner gaue good results for "dilute" solutions (XBi > 0.90) contaitzing up to six solutes. The second-order model, which includes a second-order cross-interaction term, produced a slight improvement in predictions for solutions with XZn = 0.015 and a significant improvement for solutions with XZn = 0.050 hear the limit of Henry's law region). Seveval of the quaternary solutions studied contained a total solute content of 0.215 mole fraction, and fairly good success was achieved in predicting the activity coefficient 01- zinc. ThE study of thermodynamic interactions between dilute solutes in liquid metallic solutions has occasioned much recent interest. It is useful to recall in this respect that Wagner's well-known expression for the activity coefficient' is a practical application of the problem of representing a given function, i .e., In ?, by means of a sequence of polynomials. No specific physical model of a solution is involved in its use. As suggested by Wagner, a Taylor Series is used to expand In ? about a point of infinite dilution with respect to all solutes. The partial differential coefficients of the series have been termed "interaction parameters". Various authors'-6 have proposed formalisms for parameters, the definitions being designed to meet some specific experimental or physical condition. A usual assumption is that terms above first-order in the Taylor Series may be neglected. In that case, the logarithm of the activity coefficient is expressed as a linear function of solute concentrations. The resulting expression is presumed valid for any number of additional solutes as long as the solution can be regarded as "dilute". This assumption can be termed "the hypothesis of additivity". However, experimental tests of that hypothesis for quaternary or higher-order solutions have been extremely limited. Primarily such tests have been confined to studies of effects of added metallic elements on either the activity of carbon or the solubility of gases in liquid iron.7-13 The only known previous study of an all-metal system is the limited work of Okajima and pehlke14 on the effects of multiple solute additions on the activity of cadmium in liquid lead. The present investigation is a portion of the work to determine the effects of various solute additions on the activity of zinc in dilute solution with molten bismuth in the range 450" to 650C It was shown for such ternary solutions that second-order Taylor Series terms could be evaluated at the same time as first-order terms, with no additional experimentation required. A second-order solution model was described which, under certain conditions, is a rigorous representation of solute activity in a ternary solution. (In the sense employed in this paper, the term "model", as distinguished from "equation", is taken to mean an empirical correlation or formalism, but not a hypothetical physical system per se.) Presumably such a model could be extended to produce a better representation of In ? in solutions of even higher order. The feasibility of a generalized Taylor Series approach to solution interactions and inclusion of second-order terms also has been discussed recently by Lupis and Elliott in independent work concurrent with the present investigation. In addition, they discussed empirical means of estimating certain second -order coefficients.17 The utility of such solution models rests on the ability of a truncated series to represent adequately the experimental facts in multicomponent solutions. Questions that arise include: Do the second-order terms really make a significant contribution? How far away from "dilute" solution may such models be applied? Are the types and varieties of the additional solutes important? among others. In order to provide some answers to these questions, an experimental study was made of the effects of two or more additional solutes on the activity of zinc in dilute solution with molten bismuth. Comparisons were then made with calculated activity coefficients obtained using the previously determined ternary interaction parameters. INTERACTION MODELS As an example of the approach to defining activities in multicomponent solutions, consider the Taylor Series expansion for a quaternary system, i.e., three dilute solutes. Writing terms through second order, the result is:''

Jan 1, 1968

By Noel H. Stearn

To the successful functioning of the geomagnetic method of exploration in engineering and geological practice there are two prime prerequisites : the measurability and the interpretability of significant magnetic anomalies. A magnetic anomaly may be defined as a permanent distortion of the earth's magnetic field, in order to distinguish it frog the distortions, either cyclic or irregular, which vary with time. So far as known, time fluctations have no directly assignable geologic significance in terms of rock formations, while anomalies may be considered to be directly caused by the difference in the magnetic properties within and between the formations of the substances that make up the earth's outer shell. As is effectively pointed out by L. B. Slichter,1 the effects which these differences produce on the magnetic field may be extremely minute or extremely great, depending upon the magnetic properties of the formations. Thus the actual anomalies may range from the infinitesimal to a magnitude considerably greater than that of the earth's field. The geomagnetic method of exploration has shared in the deluge of experimental effort which has lately swept geophysical prospecting to its present important place in engineering and geologic practice. But to date more of this effort has been expended upon the measurability of anomalies than upon their interpretability. The tendency has been to strive for the development of instruments and especially field techniques capable of measuring minute anomalies with a precision far beyond that for which there can be any hope of adequate interpretation other than as interesting phenomena having numerous possible causes. Such efforts, of course, are highly commendable in the field of so-called pure science, which includes the accumulation of undigested detailed observations and admits of interpretation by multiple hypotheses, but in engineering practice the factor of economy must enter. Those instruments and techniques are most desirable which can most rapidly measure the interpretable range of anomalies with the precision necessary

Jan 1, 1932

By H. H. Uhlig

Soon after general use of stainless steels began, it was observed in practice that certain combinations of factors tended to induce corrosion by pitting. For most applications this was a serious drawback, not SO much because the structural properties of the metal were impaired but because of the rapidity with which heavy sections of the alloys were penetrated by small elongated pits. These pits seemed to initiate readily in oxidizing metal salt solutions like ferric chloride and in chloride solutions like sea water. It was observed that in sea water pitting was more frequent in stagnant or polluted waters than in highly aerated, moving waters. The steels in these chloride solutions were observed to be sensitive to long contact with material such as sand grains or attached barnacles. At points of attachment or contact it was not uncommon to discover initiation of corrosion. Pits once begun at contact faces were observed to grow rapidly, usually elongating phenomenally in the direction of gravity until the metal was perforated. Hydrochloric acid and other nonoxidizing acids, on the other hand, were observed to corrode stainless steels generally; the weight losses often were higher, but the penetration less than for the pitting type of corrosion. The causes of pitting, a type of corrosion recognized as characteristic not only of stainless steels but of many additional metals and alloys, are important in corrosion studies. A possible explanation bears practical significance, for once it is known why pits begin where they do and continue to grow after initiation, intelligent direction can be given to diminishing corrosion. This can be done either by some alteration in the composition and treatment or' the alloy or by some alteration in the environment. It appears foremost in importance to discover the nature of pit foci, for if initiation of pits can be discouraged their growth will be no longer a factor to be considered. In a multi-component alloy containing many impurities normal to production of such an alloy, each of which may play a part in pitting, and whose corrosion resistance is sensitive to heat-

Jan 1, 1940

By H. H. Uhlig

Soon after general use of stainless steels began, it was observed in practice that certain combinations of factors tended to induce corrosion by pitting. For most applications this was a serious drawback, not SO much because the structural properties of the metal were impaired but because of the rapidity with which heavy sections of the alloys were penetrated by small elongated pits. These pits seemed to initiate readily in oxidizing metal salt solutions like ferric chloride and in chloride solutions like sea water. It was observed that in sea water pitting was more frequent in stagnant or polluted waters than in highly aerated, moving waters. The steels in these chloride solutions were observed to be sensitive to long contact with material such as sand grains or attached barnacles. At points of attachment or contact it was not uncommon to discover initiation of corrosion. Pits once begun at contact faces were observed to grow rapidly, usually elongating phenomenally in the direction of gravity until the metal was perforated. Hydrochloric acid and other nonoxidizing acids, on the other hand, were observed to corrode stainless steels generally; the weight losses often were higher, but the penetration less than for the pitting type of corrosion. The causes of pitting, a type of corrosion recognized as characteristic not only of stainless steels but of many additional metals and alloys, are important in corrosion studies. A possible explanation bears practical significance, for once it is known why pits begin where they do and continue to grow after initiation, intelligent direction can be given to diminishing corrosion. This can be done either by some alteration in the composition and treatment or' the alloy or by some alteration in the environment. It appears foremost in importance to discover the nature of pit foci, for if initiation of pits can be discouraged their growth will be no longer a factor to be considered. In a multi-component alloy containing many impurities normal to production of such an alloy, each of which may play a part in pitting, and whose corrosion resistance is sensitive to heat-

Jan 1, 1940

By P. B. Bucky

In previous publications1 it was shown that a scalar model of any weighty structure, where the stresses produced are mainly due to gravitational forces, will behave similarly to its prototype if the model and prototype material are the same and the model is placed in a centrifugal field of force (substituted for the gravitational field) which has been increased in the same proportion as the linear model scale is decreased. This principle is now being applied to a study of the behavior of mine structures in an attempt to determine the laws that control them. The importance of using models as a means of solving mining problems has been discussed previously, yet it may be well to reiterate here that this method of research and type of solution have been productive of far-reaching results in other engineering fields, notably those of hydraulics and aerodynamics. Model research is a comparatively cheap and time-saving method of checking practical experience. Up to the present time the best guide to what will happen underground has been the judgment of the man who has observed most and been longest acquainted with the local conditions. His experimental work underground is limited by the elements of cost, time and danger, while failure is seldom permissible. In a model, as in a test tube, all elements that affect the solution of a problem are under definite control. Each element may be varied independently at hill and its effects noted. Experimental work on a small-scale model may therefore be performed at a comparatively small expenditure of time and money, instead of on a full scale in the mine, where the cost, time, and danger elements are necessarily great. The experiments described in this paper are to be considered as part of a progress report and a continuation of Technical Paper 425. One object of the research program is to make each experiment point the way for further research on that particular phase of the general problem. The results and conclusions presented here are therefore not to be considered as final, but arc to be interpreted as

Jan 1, 1934

By P. R. Kalischer

In the production of alloys by powder metallurgical processes it is often necessary or desirable to include one or more cornponents that tend to form very stable oxides. Included in this group of metals are aluminum, manganese, magnesium, silicon, and a few others. In many cases it is not necessary for the sintered compact to have full density and the other physical characteristics of a cast alloy and in that event no undue precautions need be taken. If, however, it is required that the sintered part be entirely homogeneous, and have maximum density and physical properties, some method must be found to reduce the surface films of oxide, which are always present on the metals, and for the metals mentioned above this is always extremely difficult, if not impossible. since the production of high-density alloys is of particular interest to powder metallurgists, some experiments were undertaken to devise methods of reducing the refractory oxides. For this work, alloys of iron, nickel, and aluminum were chosen because aluminum oxide is one of the most stable oxides and because these alloys in the right compositions form excellent permanent magnets. All of the pertinent properties of the magnets could be accurately and delicately measured by density measuremerits and magnetic tests of sufficient scope to give a complete demagnetization curve. From such a curve the maximum coercive force, residual magnetism, and energy products could be obtained and compared with the same properties for a cast material. Any lack of homogeneity, density, or solid diffusion would be immediately apparent as a decrease in the magnetic properties. Nature and Removal of Surface Barriers The early work of the present investigation was based upon published processes.* In the published information it was claimed that by intimately mixing iron, nickel, and iron-aluminum alloy (50 Per cent Fe, So Per cent Al) powders, compressing such a mixture into the desired shape and size, and then sintering (heating to a temperature below the melting point of the component metals) in hydrogen at 1200°C. or higher, a sound, homogeneous article could be made having the desired physical size, shape, and strength, and good magnetic characteristics. However. this early work showed clearly that something in the powder compress was inhibiting diffusion and the process was almost entirely unworkable. In the initial phase of the investigation samples of iron powder, nickel powder, and iron-aluminum alloy powder were pressed into separate bars and sintered in hydrogen. Both the iron and nickel powders sintered

Jan 1, 1941

By P. R. Kalischer

In the production of alloys by powder metallurgical processes it is often necessary or desirable to include one or more cornponents that tend to form very stable oxides. Included in this group of metals are aluminum, manganese, magnesium, silicon, and a few others. In many cases it is not necessary for the sintered compact to have full density and the other physical characteristics of a cast alloy and in that event no undue precautions need be taken. If, however, it is required that the sintered part be entirely homogeneous, and have maximum density and physical properties, some method must be found to reduce the surface films of oxide, which are always present on the metals, and for the metals mentioned above this is always extremely difficult, if not impossible. since the production of high-density alloys is of particular interest to powder metallurgists, some experiments were undertaken to devise methods of reducing the refractory oxides. For this work, alloys of iron, nickel, and aluminum were chosen because aluminum oxide is one of the most stable oxides and because these alloys in the right compositions form excellent permanent magnets. All of the pertinent properties of the magnets could be accurately and delicately measured by density measuremerits and magnetic tests of sufficient scope to give a complete demagnetization curve. From such a curve the maximum coercive force, residual magnetism, and energy products could be obtained and compared with the same properties for a cast material. Any lack of homogeneity, density, or solid diffusion would be immediately apparent as a decrease in the magnetic properties. Nature and Removal of Surface Barriers The early work of the present investigation was based upon published processes.* In the published information it was claimed that by intimately mixing iron, nickel, and iron-aluminum alloy (50 Per cent Fe, So Per cent Al) powders, compressing such a mixture into the desired shape and size, and then sintering (heating to a temperature below the melting point of the component metals) in hydrogen at 1200°C. or higher, a sound, homogeneous article could be made having the desired physical size, shape, and strength, and good magnetic characteristics. However. this early work showed clearly that something in the powder compress was inhibiting diffusion and the process was almost entirely unworkable. In the initial phase of the investigation samples of iron powder, nickel powder, and iron-aluminum alloy powder were pressed into separate bars and sintered in hydrogen. Both the iron and nickel powders sintered

Jan 1, 1941

By Herbert Hoover, Harlod Washburn

This paper is in the nature of a rough preliminary report on the progress that has been made in the application of the mass spectrometer to various problems arising in the petroleum industry. A few years ago the authors considered a number of the problems that were arising in the qualitative and quantitative measurement of small amounts of hydrocarbons. The methods available of making analyses by chemical techniques appeared to leave much room for improvement. Without going into the reasons at this point, attention was turned to the possibility of employing physical instead of chemical methods of accomplishing the desired results. A preliminary investigation disclosed that the mass spectrometer presented a possibility of solving many problems which could not easily be accomplished by other methods. Work was begun in developing the necessary apparatus and technique. A great deal of encouragement and many valuable suggestions were received from Dr. Robert A. Millikan, Dr. W. R. Smythe, and Dr. W. N. Lacey, of the California Institute of Technology, and from Dr. E. 0. Lawrence, who recently received the Nobel Prize, of the University of California. The authors particularly wish to acknowledge the very great willingness of these outstanding scientists to be helpful in solving many of the problems that were involved. So far as the authors are aware, this was the first application of the mass spectrometer to commercial work. The results were considerably better than had at first been anticipated. Briefly, it is possible to run a qualitative and quantitative analysis of an unknown mixture of hydrocarbon gases, with an accuracy of better than plus or minus 5 per cent of each of the various constituents. An exceedingly high degree of sensitivity has been obtained, and a relatively short time is required to complete an analysis. Furthermore, it is unnecessary to separate a mixture of gases into its various components in order to complete the analysis. The Mass Spectrometer The mass spectrometer should not be confused in any way with the optical 01 grating type of spectrograph now in general use. The operation of the mass spectrometer is entirely different in principle and bears practically no resemblance to the optical or grating instruments. The original conception and development of the mass spectrometer dates from and is generally credited to Aston, of Cambridge, England. An early accomplishment of his research, about 20 years ago, was the discovery that the inert gas neon was actually a mixture of two kinds of atoms, one of the atomic weight 20 and the other of atomic weight 22. These two components occurred mixed in such proportion as to yield the usual atomic weight of 20.2. The study was continued and most of the elements were shown to be mixtures of components whose atomic weights can, to in

Jan 1, 1941

By Harlod Washburn, Herbert Hoover

This paper is in the nature of a rough preliminary report on the progress that has been made in the application of the mass spectrometer to various problems arising in the petroleum industry. A few years ago the authors considered a number of the problems that were arising in the qualitative and quantitative measurement of small amounts of hydrocarbons. The methods available of making analyses by chemical techniques appeared to leave much room for improvement. Without going into the reasons at this point, attention was turned to the possibility of employing physical instead of chemical methods of accomplishing the desired results. A preliminary investigation disclosed that the mass spectrometer presented a possibility of solving many problems which could not easily be accomplished by other methods. Work was begun in developing the necessary apparatus and technique. A great deal of encouragement and many valuable suggestions were received from Dr. Robert A. Millikan, Dr. W. R. Smythe, and Dr. W. N. Lacey, of the California Institute of Technology, and from Dr. E. 0. Lawrence, who recently received the Nobel Prize, of the University of California. The authors particularly wish to acknowledge the very great willingness of these outstanding scientists to be helpful in solving many of the problems that were involved. So far as the authors are aware, this was the first application of the mass spectrometer to commercial work. The results were considerably better than had at first been anticipated. Briefly, it is possible to run a qualitative and quantitative analysis of an unknown mixture of hydrocarbon gases, with an accuracy of better than plus or minus 5 per cent of each of the various constituents. An exceedingly high degree of sensitivity has been obtained, and a relatively short time is required to complete an analysis. Furthermore, it is unnecessary to separate a mixture of gases into its various components in order to complete the analysis. The Mass Spectrometer The mass spectrometer should not be confused in any way with the optical 01 grating type of spectrograph now in general use. The operation of the mass spectrometer is entirely different in principle and bears practically no resemblance to the optical or grating instruments. The original conception and development of the mass spectrometer dates from and is generally credited to Aston, of Cambridge, England. An early accomplishment of his research, about 20 years ago, was the discovery that the inert gas neon was actually a mixture of two kinds of atoms, one of the atomic weight 20 and the other of atomic weight 22. These two components occurred mixed in such proportion as to yield the usual atomic weight of 20.2. The study was continued and most of the elements were shown to be mixtures of components whose atomic weights can, to in

Jan 1, 1941

By W. B. Hincke, C. G. Maier

Commercial processes of lead softening directly involve the behavior on fusion of mixtures of the oxides of antimony and lead, and the vapor pressures of these materials. Practically no quantitative data have been available for the discussion of lead softening from the point of view of the fundamental metallurgy of the process. The Pacific Experiment Station of the United States Bureau of Mines, in cooperation with the University of California, in the course of its program of study of the fundamental properties of oxides and sulfides, recently made vapor pressure measurements upon the various forms of pure antimony trioxide.1 When these measurements were considered in connection with the softening and "fuming" furnaces which are often used for lead purification, an unexpectedly anomalous condition appeared. In brief, this anomaly consisted in the fact that in certain softening furnaces, where lead bullion of approximately 1 per cent antimony content was being treated at a temperature of approximately 1300" F., no appreciable volatilization of antimony occurred, there being produced only a "skim" containing from 15 to 20 per cent Sb, 65 to 60 per cent Pb, as mixed oxides. In the "fuming furnaces," where the temperature was only about 1400" F. and where an accumulation of "skims" from the primary softener was being treated with certain other antimony-containing materials, a considerable volatilization of antimony as oxide occurred; an "impure" skim of some 60 to 65 per cent Sb and 10 per cent Pb was also produced as mixed oxides. The latter material cannot be suitably treated in hearth-type or softener furnaces. The essential chemical difference between the first and second step is the customary use of some reducing material (such as petroleum coke) in the later operation. An obvious interpretation of the effect of coke in facilitating the fuming of the antimony is the supposition that the antimony may be reduced to metal, and volatilized as such. This supposition is improbable, however, when it is realized that a slight extrapolation of the vapor-

Jan 1, 1932

By S. L. Hoyt

Some of the more important properties of finished materials are strength, ductility, toughness, resistance to alternating and repeated stresses, etc. Of these, the property that appears to have received the least consideration, at least in this country, is toughness, which is due, possibly, to our regarding toughness as a qualitative property or, at any rate, as one that parallels ductility. This arises out of our greater experience with the simple carbon steels in the rolled or forged (non-heat-treated) condition which, qualitatively, are tough if ductile and are not tough if brittle. In this way we have erroneously become accustomed to judging the toughness of a material from its behavior in the tensile or similar test. The point of view presented in the present paper is that toughness, like hardness or tensile strength, should be regarded as an independent property and of sufficient importance to require, in so far as that may be possible, quantitative determinations. If such be true, it becomes at once necessary to devise experimental means for measuring or valuating toughness, and the notched-bar impact test (the Charpy test) is advanced as the most logical test that has so far been developed for this purpose. It is further advanced, with particular emphasis, that we have two kinds of toughness to deal with and, accordingly, they will be dealt with independently. Classification of Materials According to Toughness Toughness has been defined somewhat as follows: Tough materials are those that offer considerable resistance to permanent deformation but which, once such resistance has been overcome, may be deformed plastically, but only by the expenditure of considerable energy. In other words, tough materials may be deformed plastically but they absorb a considerable amount of work in the process. This kind of toughness may be called "static" toughness when the rate of loading is reasonably slow or "dynamic" toughness when the rate of loading is comparatively rapid, as in impact testing, but in all cases the stress distribution is essentially uniform. However, static toughness does not

Jan 1, 1920

By W. S. Landis

In brief, this is the story of an attempt to Americanize a process originally developed in Europe. The story will be recited in two sections, the first dealing with the process as developed by the European engineers; the second containing the improvements and modifications of American origin, together with some details of the operating results of the unit as finally assembled. Developments in other directions in this same field have not, up to the present, pointed out an economic future for the process, therefore our record here is largely a report of development progress. Whether some particularly favorable location will be found at some future time for a commercial installation cannot as yet be foretold. The project is now at a standstill. The peculiar tools of the electrometallurgist should be of great interest to the zinc smelter. The low thermal efficiency of the zinc retort, its comparatively small-scale unit and its intermittent cycle as it stood in 1925, should make this art a particularly fertile field for the electric furnace. Yet in spite of years of work recorded in volumes of literature, and an expenditure of large sums of money, there is not a single electrothermic zinc smelter operating anywhere in the world. In this industry the electric furnace plays only a secondary part today. Historical The first serious proposal to use the electric furnace for the smelting of zinc ores was made by the Cowles Brothers in 1885, but their experimental work did not advance the art to any extent. The next investigator of this field was Dr. Gustav DeLaval, a Swedish engineer well known to the industrial world through his development of the centrifugal and the steam turbine. The DeLaval cream separator is a familiar household appliance in most parts of the world. Although Dr. DeLaval commenced his experiments in the field of electric zinc smelting in 1893, it was not until 1898 that he had a practicable furnace, even then operating but intermittently. His work was done at Trollhättan, Sweden. He continued to improve this early fur-

Jan 1, 1937

By Frederick Mark Becket

DOCTOR Albert Sauveur, distinguished scientist and Honorary Member of this Institute, predicted in the first Howe Memorial Lecture that the privilege of delivering this annual address would be considered a highly significant honor. The intervening years have well borne out Sauveur's prophecy. I wish to assure the American Institute of Mining and Metallurgical Engineers that I also deeply appreciate this honor, recognizing at the same time the present and even more the future responsibilities with which it is accompanied. Several of the previous lecturers had the good fortune to attend the classes of Professor Howe and to work in his laboratories. I was similarly favored, although in my instance and to my great regret the period was all too short. However, Howe's book, published in 1903, "Iron, Steel and Other Alloys," afforded me abundant opportunity to continue these studies. How well I remember the inspiration I derived from this famous book by Howe, the metallurgical master, pioneer, and educator! Remembering that Professor Howe contributed numerous papers to The Metallographist, a magazine supported from a technical point of view by the world's pioneers in metallography, I was curious a few days ago to learn the nature of Howe's early contributions to this magazine. The first paper by Howe in the first year of The Metallographist (1898) dealt with the allotropic theory; the second also treated of allotropy, and I quote the first sentence of that paper: The allotropic theory of the hardening of steel may, like so many other important theories, have to be accepted or rejected not on direct proof or disproof, but on the accumulation of circumstantial evidence for or against it. Howe's ability to stimulate others by his deep understanding and clarity of expression was truly remarkable; but just as striking was his intuitive judgment concerning the implications of metallurgical data in the arts and sciences. It therefore seems fitting that this lecture comprise a broad treatment of the subject chosen, rather than a closely documented thesis on any one phase of the problem; that in it attention be focused

Jan 1, 1938

By J. W. Martin, L. K. Singhal

Grain boundary M23CB precipitates have been shown to form by a process involving the migration of an austenite grain boundary, and each plate of precipitate is in parallel orientation with one of the austenite grains constituting the boundary. The carbide distribution and morphology appear to be sensitive to grain boundary mis orientation. Some areas of austenite grain bowzdary permit the development of an array of M,C, particles, some of which are in parallel orientation with one grain and some with the other grain constituting the boundary. Massive carbide at grain boundary triple points is also shown to be in parallel orientation with one constituent grain. PREFERENTIAL precipitation during aging of carbides of the type (Fe,Cr)23C6, usually written MZ3C6, in grain boundaries of quenched austenitic stainless steels has been widely recognized. M23C6 has a complex cubic crystal structure' which contains ninety-two metal atoms and twenty-four carbon atoms per unit cell. Less energy is involved in forming grain boundary precipitates than in the formation of intragranular precipitates, and the process is further enhanced by the accelerated diffusion rates in the boundaries and by the probability of segregation of chromium atoms and carbon atoms to the region of the grain boundaries during prior solution heat treatment in order to reduce lattice strain. Early electron micrographic studies2, 3 involving either extraction replica or normal replica techniques established the geometric or dendritic form of the carbide particles, although this approach led to dis- pute as to whether the particles grew within the plane of the boundary or grew into the matrix.4-6 More recent thin-foil studies' have claimed to identify a discontinuous precipitation process involving M23C6 at grain boundaries, and the object of the present work was to attempt to clarify the situation using modern electron micrographic and diffraction techniques. 1) EXPERIMENTAL 1.1) Material. The steel selected for this work had a base composition of 24 pct Ni-25 pct Cr-3 pct Ti and contained about 0.04 pct C. The full analysis if given in Table I. This alloy was in the form of strip which had been hot- and cold-rolled to a thickness of 0.6 mm. 1.2) Heat Treatment. Specimens 4 cm long by 1 cm wide were solution-heat-treated for 3 hr in argon at 1150°C, followed by water-quenching. Specimens were subsequently aged in vacuo at 750°C for periods up to 500 hr. 1.3) Preparation of Electron Microscope Specimens. The heat-treated strips were cut bv spark machining into discs of 3 mm diam and 0.6 mm thickness. he-discs were dished on both sides using an electrolytic jet of 15 pct HCl electrolyte at 80 v. Final electro-polishing of the discs was carried out using 10 pct perchloric acid, 20 pct glycerol, and 70 pct ethanol at 10 v. The current density was kept below 300 ma. cm"2 by cooling the electrolyte to 0" to 5°C. As soon as a small hole appeared, the electropolishing was stopped and the specimen was quickly washed with ethanol.

Jan 1, 1969

By R. W. Fountain, W. D. Forgeng, G. M. Faulring

Precipitation of the phase Co3Ti (Cu3Au type) from a Co-5 pct Ti a11oy has been investigated using single-crystal X-ray diffraction techniques. Oscillation and transmission Laue patterns of specimens aged for short-time periods at 600" C indicate the formation of titanium-rich and titanium-poor zones coherent with the {100} matrix planes. Longer aging times at 600° C establish that the equilibrium phase also forms on the {100} matrix planes as platelets. These observations are corroborated by electron metallography; electron diffraction studies show the phase Co3Ti to be ordered. A probable sequence of the precipitation reaction is discussed. A previous publication by two of the present authors reported on the phase relations and precipitation in Co-Ti alloys containing up to 30 pct Ti.1 The results of this investigation established the existence of a new face-centered cubic inter metallic phase, ranging in composition from about 17.0 to 21.7 pct Ti at temperatures below 1000° C The decomposition of the fcc supersaturated solid solution was studied employing hardness and electrical resistivity measurements. The changes in hardness upon precipitation in alloys containing 3, 6, and 9 pct* Ti were found to be associated with an initial increase in hardness followed by a plateau and then a second, more pronounced hardness increase. Investigation of this behavior by electrical resistivity measurements suggested that two different kinetic processes were involved, which, when interpreted in terms of the kinetic relation,2-4 indicated that initial precipitation was in the form of thin plates. On continued aging, the plates impinged during the growth process. The general features of these findings have been confirmed by Bibring and Manenc,5 while, in addition, they report the phase to be ordered. The present investigation was undertaken to provide more definite information on the structural relationships between the precipitate and the matrix. EXPERIMENTAL PROCEDURE Single crystals of a (20-5 pct Ti alloy were prepared from the melt employing the Bridgman technique. Poly crystalline rod, 1/2 in. in diam, prepared from vacuum-melted material, was machined to 3/8- in. diam to remove any surface contamination that may have resulted from hot-working. The crystals were grown under a purified hydrogen atmosphere in high-purity alumina crucibles heated by induction. Considerable difficulty was encountered in attempting to grow monocrystals because of the high melting point of the alloy and the high solute concentration. However, one crystal about 6 in. long was obtained which was essentially a single crystal except for one or two very small grains around the periphery. The as-grown crystal was solution heat-treated for 24 hr at 1200°Cin a purified argon atmosphere and water-quenched. One-quarter-in. slices were taken from each end of the solution heat-treated crystal for chemical analyses, and the remainder of the crystal was mounted and oriented by the back reflection Laue Method. The chemical analysis of the crystal was as follows: Pct Ti Pct 0 Pct C Pct N Pct H Pet CO 5.29 0.08 0.004 0.002 0.0003 Balance By proper tilting of the crystal, it was possible to obtain slices 1/32 in. thick of [loo] and [110] orientation. The solution heat-treated crystal slices were sealed in silica capsules for the aging treatments, with titanium sponge placed at one end of the capsule to act as a getter. All slices were water-quenched from the aging temperatures, the capsules being broken under the water to ensure a rapid quench. Thinning of the slices for transmission X-ray studies was accomplished by a combination of mechanical and electrolytic techniques, the final thickness being about 0.1 mm. Laue patterns of the solution heat-treated crystal indicated that no strain was introduced by the thinning technique. ELECTRON METALLOGRAPHY After X-ray examination, the structural changes attending the precipitation were followed by examination of direct carbon replicas of polished and etched surfaces of the single-crystal slices and extracted phases. The earliest indication of significant structural change was observed after aging at 600°C The structure of a heavily etched, solution-treated crystal is shown in Fig. l(a). Aside from the etch pit pattern, no regularity of background structure is observed. On the other hand, in the background of the specimen heated for 500 hr at 600°C, the etching pattern shows a directionality indicating the influence of minute precipitate particles, Fig. l(b). On electrolytic dissolution of this specimen in 10 pct HC1 in alcohol, a large volume of very small, flattened cubes

Jan 1, 1962

By F. B. Plummer

PERHAPS the greatest progress made in the technical methods of oil production during the last year has been in handling gas from the new fields that yield light distillate fractions. At least sixteen recycling plants have been perfected and installed in South Texas fields alone during 1939 having a daily capacity of more than one billion -2 cubic feet of gas and capable of producing more than a million gallons of distillate daily. The process consists of running the gas under pres- sure through especially designed plants, separating out the condensate, then compressing the gas to 3000 lb. or more, depending on the subsurface pressure in the formation, and injecting gas back into the reservoir to be produced again later, along with more of the liquid hydrocarbons, and again recycled. Hence production in these distillate fields in sense has changed from that of producing a constantly diminishing and much-wasted product to a more or less continuous manufacturing process, in which practically all the gas is conserved-a real triumph in engineering practice.

Jan 1, 1940