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By S. Leber, R. F. Hehemann

This investigation describes the kinetics of alloying in a (Cb-15 wt pct W. 5 wt pct Mo, 1 wt pct Zr) powder-metallurgy alloy. The degree of homogeneity obtained in hydrostatic ally pressed and vacuum-sintered samples is described by composition distributions resulting from analysis of X-ray dvfraction line profiles. Sintering variables and degvee of powder dispersion were evaluated. The utility of single-value parameters obtained from composition distributions is disaissed. The spatial distribution of composition, as revealed by anodically tinted metallographic sarrzples, was used to provide diffision models based on a concentric-sphere geometry. Diffusion equations developed from these models were found to be in general agreement with experimental results. The powder-metallurgy method for the production of refractory metal alloys has the ability to produce an inherently fine-grained, fabricable structure. The more general use of this method is inhibited, in part, by the presumed difficulty in obtaining homogeneity on a microscale. The degree of homogeneity therefore is an important, but usually neglected, variable in specifying the quality of a powder-metallurgy alloy. Convenient techniques for measuring the degree of homogeneity are now available,' and have been used to develop a model describing the process of alloying in a simple binary mixture.' In this investigation, the process of alloy formation has been studied in a more complex system. PROCEDURE The columbium-based F-48 mixture was prepared from the constituent powders shown in Table I. The particle sizes tabulated were provided by the vendors of the individual powders. Standard laboratory techniques utilizing a jar mill were employed for blending. The blended powders were hydro-pressed into 1-in. diam rods which were then sliced into thin discs for vacuum sintering. All samples were given a preliminary treatment at 1700°C for 2 hr. Varying degrees of homogeneity were obtained using additional treatments at higher temperatures. The degree of homogeneity obtained by a specific sintering treatment was evaluated metallographi-cally using the anodic-tinting technique described by olff,' and quantitatively by the analysis of X-ray diffraction line profiles using the X-ray diffraction technique developed by udman.' The diffraction technique is strictly valid only for binary systems. However, the relatively small difference between the lattice parameters of tungsten and molvbdenum when compared with columbium permitted the treatment of the complex composition of F-48 as a (W, Mo)-Cb pseudobinary. Calculations were weighted in accord with the W-Mo ratio in the F-48 composition. The contribution of the 1 pct Zr was ignored since it could not even be detected in the blended powder. Two factors are required to convert an X-ray line profile into a composition distribution. The variation of these factors with composition is shown in Fig. 1. Curve A was used to convert angular posi-

Jan 1, 1964

By B. J. Shaw, R. Kossowsky, W. C. Johnston

High purity (99,95) Ni-51 wt pct cr eutectic alloy was unidirectionalty solidified at rates of 0.1 to 8 in. per hr. The resulting material was characterized by large grains, approximately 0.5 mm in cross section and extending through almost the entire length of the specimen, parallel to the growth axis. The eutectic structure of specimens the growth at -1/3 The per hr consisted of a continuous nickel-rich phase and chrome -rich lamellae approximately 2 thick, spaced about apart. Specimens were tested in compression at temperatures ranging from —196 to 850"C over which range the 0.2 pet yield strength dp -creased from 160,000 p si to 35,000psi, respectively. Swaging to 40 pet reduction in area, followed by a 30-min anneal at 1000c to remove residual cold work, increased the 0.2 pet yield to 260,000 psi at -196°C, dropping to 35,000 psi at 850°C. The increase in strength was attributed to a residual cell structure. The strength of the alloy could be rationalized by the simple rule of mixtures if one assumed that additional strength is derived front a size effect characterized by is petch equation IN recent years there has been increasing interest in dispersion and second phase strengthening in materials needed for high-temperature applications. inm role of structure on the mechanical The of such alloys has been well established of such some extent accounted for theoretically. and to of how the strengthening mechanisms due to fibers and lamellae operate has been reduced to its fibers form by the fabrication of composites of strong rods unidirectionally aligned in a From work on tungsten-fiber-reinforced copper, for example, it was established that the "Rule of Mixtures" could explain the strengthening.12 " some what more sophisticated technique for introducing strong fibers into copper matrix was used by Hertzberg strong Kraft3 who unidirectionally solidified the copper-chromium eutectic. The use of unidirectionally fied eutectics has advantages in that there are no matrix-fiber wetting problems and fine fibers are automatically aligned and uniformly fiber However, one Is restricted to a specific volume fraction of the second phase. Nevertheless, even though the volume fraction is fixed, the rod or lamella thickness, , can be varied by controlling the freezing interface velocity. Alternatively, the grown material may be worked down by swaging or rolling. Embury and Fisher, " using this approach, drew down pear lite in iron and studied the mechanical properties iron and that the yield strength, oy, was properties.proportional They that d was the wire diameter. It could be inferred that was also proportional to but the work hardening had to be taken into consideration at the same time. By varying the growth rate of the cadmium-zinc lamellar eutectic, Shaw'1 showed that was proportional to without the introduction of work hardening and suggested that the lamellar interface itself contributed to the strengthening of the composite. In this investigation we have evaluated the mechanical properties of the unidirectionally solidified fec-bec eutectic Ni-Cr. This eutectic was selected because it presented the possibility was selected beca temperature, and high corrosion resistant alloy, and also represented a hard-soft phase combination with two completely different slip systems. Specimens were tested in compression and tension up to 850°C and a detailed study of the micro structure as a function of plastic strain and temperature was carried out by light and electron microscopy. It was shown that the composite strength tested in compression can be accounted for by the simple rule of mixtures if one allows for an additional term representing the effect of Intereprese EXPERIMENTAL PROCEDURE 1) Unidirectional Solidification. Fig. 1 is a schematic drawing of the apparatus used to produce 0.2 in. diam by 12 in. long alloy ingots. The crucible tube is alumina, containing the charge which has been is swaged, or machined to 0.195 in. diam. The lower end of the tube is immersed to 0 .195in in.d iam. The upper end is supported by a 10 mil nichrome wire which lowers the crucible mil nic hr the] wire at a prescribed rate. Surrounding the furnace is a graphite susceptor into which a control thermocouple is inserted. The furnace is insulated with fiberfrax and enclosed in a quartz tube. There is a sliding seal at the bottom around the crucible and one on the top so that an atmosphere may be used for the sample and suscep tor. The power for the furnace is supplied from a 10-kw, 450 kc generator. The skin depth (the skin depth at which the field falls to l/e of its value at the outer surface) for graphite (p = 10 (j-ohm-cm) is 0.1 in. at this fre-

Jan 1, 1970

By Edward Thomas

THE late George S. Rice was active in the investigation of bumps, particularly in the last ten years of his career as chief mining engineer of the U. S. Bureau of Mines. Since most of his investigation was carried out in Great Britain, continental Europe, and-to a lesser extent-Canada, his thinking on prevention was influenced considerably by the experience of those countries. It is not surprising, therefore, that when he was called upon a few years before his retirement to investigate bumps in the U. S. and suggest ways to prevent them, he turned to longwall mining. A longwall method had been most successful in combating the bump hazard in mining coal under deep cover, especially in Great Britain, but the prevailing method there at the time was advancing longwall mining, which he knew was uneconomical under U. S. mining conditions. For this reason he proposed a modified retreating longwall system that he believed included the best features of the advancing method. As brought out by Rice,1 if the cover is 2000 ft and 50 pct of the coal is extracted, the static load on the remaining pillars will be about 4000 psi, which exceeds the ultimate crushing strength2 in most instances. If the pillar coal is overloaded before a pillar line is established, then the abutment zone preceding a line of extraction is no place to split pillars or extract them by any method other than an open-end system. Rice therefore advocated open-end mining, preferably by longwall, but he was willing to compromise with long-face mining if the longwall method was not acceptable.

Jan 8, 1958

By D. J. Carney, C. W. Boquist, E. C. Rudolphy

Effect of variations in sinter feed composition on sinter strength, bulk density, re-ducibility, chemical composition, and microstructure were determined by sintering experimental samples on a production sintering machine. Increasing amounts of roll scale, ore fines, return fines, and blast furnace slag were most beneficial to feed permeability, sinter bulk density, and strength. Burnt lime additions improved feed permeability but were not beneficial to sinter strength or bulk density. Sinter reducibility was adversely affected by all additives. DEVELOPMENT of methods for evaluating sinter quality, which would in some way predict the behavior of the sinter during charging and smelting in the blast furnace, has been given considerable attention in recent years. In a previous investigation at South Works of the United States Steel Corp., standard sinter sampling and testing procedures were developed.1,2 By modifying the sinter sampling device, a method of sintering experimental mix sinter samples upon a production Dwight-Lloyd sintering machine was also developed. This technique afforded a rapid and controlled method of investigating the effects of the various raw materials and additives on sinter quality and was used in this present investigation. Since the beginning of the present study in 1953, the results of numerous sinter investigations have been published, most of which were concerned with production tests of iron ore sinter, both here and abroad. Three groups of investigators reported results of experimental sinter studies that were related to this investigation. Voice et al.3 studied the effects of controlled variables on sinter quality by producing and testing experimental Northants iron ore sinter using an experimental sintering unit. Mor-rissey and Powers' determined the relationship between iron ore sinter quality and the moisture and coke content using a small laboratory sintering system. Burlingame et al.5 studied the effects of "additives" upon iron ore sinter using a laboratory sintering apparatus and laboratory grade raw materials. At South Works, it was considered desirable to study the effects of sinter mix composition and additives upon the quality of a flue dust-base sinter produced on a production sintering unit. Extrapolation of controlled laboratory test data to sintering plant operation lacking such precise control is not altogether satisfactory. Therefore, the present study was conducted in a manner which approximated production conditions as closely as possible. The raw materials used were those commonly encoun- tered in the production of flue dust and flue dust ore-type sinters and these were varied within extremes encountered in this type of sinter production. Experimental Procedure The experimental sinters were produced from 100 lb mixtures of sinter feed. The principal raw materials and additives used, their particle size, and approximate chemical composition are listed in Table I. The mixing of the raw materials was accomplished by means of a miniature single shaft pug mill shown in Fig, 1. The use of the pug mill as a mixer was decidea upon after encountering difficulty in reproducing the mixing and chopping effect of the sinter plant pug mill with other types of available small mixers. The miniature pug mill was constructed, consisting of 31/2x2x1/4 in, blades spaced 3 in. apart along a 3 ft shaft. Preliminary tests were run with this small mixer to establish the proper rotation speed and the required number of passes through the pug mill to thoroughly mix and distribute all the raw materials in a manner approximating the production Pug mill- Although the effects of varying the mosture content were determined in one particular series of tests, the amount of moisture added was changed as the composition of the experimental mix was varied. The aim in making water additions was to achieve a permeability as high as possible for each particular

Jan 1, 1956

By W. M. Rust, W. D. Mounce

THE almost universal acceptance of electrical logging by the petroleum industry calls for a critical examination of the physical bases of the common methods. This is particularly needed for the natural potential log. The conventional explanations are based on the phenomena of electrofiltration and electro-osmosis. However, experimental data show that they fail to give a basis that is quantitatively sound. Moreover, they lead to interpretations of details of electrical logs that are erroneous. It was found experimentally that when a plug of shale is placed in a chain of dissimilar electrolytes, a current flow results. Experiments on oil-well cores and fluids similar to those existing in wells show that potentials are set up which are in reasonable agreement with those encountered in electrical logging. Doubt- less other sources of potential are important but this explanation not only accounts for much of the potential but also clarifies some fairly familiar examples of misinterpretations.

Jan 1, 1944

By G. Pizzi, G. M. Ciucci, G. L. Chierici

The use of the material balance equation to estimate the volume of hydrocarbons originally present in a reservoir, whose producing mechanism is partly due to water drive, has been discussed in the literature by several authors. There is no general agreement upon the possibility of obtaining reliable results by this method. Gas reservoirs in contact with an active aquifer are considered in this paper. Theoretical considerations based on the cybernetic principle of uncertainty (which states that the internal structure of a system cannot be uniquely determined from its observed external behavior) lead to the conclusion that the volume of gas originally present in a reservoir of this type cannot be uniquely determined from its past history. The range of values which encompasses the actual value of the reserves varies from case to case and must be determined by either numerical or analogical methods. Results obtained for six gas fields are reported. All these fields were produced with small fluctuations in their production rates, as is common practice for gas reservoirs; no gas storage fields were considered. Results obtained show that reserves values in a range of 1 to 2, associated with appropriate aquifers, allow the matching of the reservoir past history with mean-square deviations less than the experimental errors involved in pressure and produclion measurements. Similar results have been found in several other partial water drive gas reservoirs. From these results it is concluded that gas reserves cannot be uniquely determined from the past performance of partial water drive reservoirs, at least in cases where the reservoir has been submitted to small fluctuations in the production rates, and pressure data of normal accuracy are available. INTRODUCTION A number of authors have analyzed the problem of estimating the reserves originally present in a partial water drive reservoir from its past pressure-production performance. Literature which deals with this subject can be grouped, according to their conclusions, as follows. 1. A reliable value for the reserves can be obtained even if reservoir data (pressure and cumulative production) are affected by errors within the normal range.'-' 2. A reliable value for the reserves can be obtained only if reservoir data are very accurate'- or if past production performance has been subjected to abrupt variations in the production rate."' 3. No unique value for the reserves can be obtained from reservoir past production performance. This conclusion has been based upon theoretical considerations" and verified in several field cases. The purpose of this paper, which deals only with partial water drive gas reservoirs, is to test the above conclusions against actual field cases. Some theoretical considerations on this problem are also presented. THEORETICAL CONSIDERATIONS As the behavior of a gas reservoir communicating with an aquifer depends on both the aquifer and the reservoir characteristics, the physical system to be studied is the combined gas reservoir plus aquifer. The information which is available for studying the performance of such a system is the well production rates and bottom-hole pressures, all given as functions of time. The external behavior of the reservoir-aquifer system is therefore described by 2n input variables (Gp, Wp,) and n output variables (p,), n being the number of wells in the reservoir. In reservoir engineering it is common practice to consider the reservoir as a whole, disregarding the internal distribution of pressures and of producing wells. This practice is equivalent to substituting the above multi-variable system with a single-variable system, where the average reservoir pressure is the only output variable and the cumulative production G,(t) and W,(t) are the input variables. The internal structure of such a system, defined by initial gas reserves G, aquifer shape and dimensions, boundary conditions and petrophysical parameters distribution throughout the aquifer, is unknown. Therefore, from a cybernetic point of view the system is a "black-box It has been demonstrated" that for a blackbox the indetermination principle holds. Accordingly, the number of different internal structures (or set of parameters) which can account for the observed external behavior is infinite. As a consequence, the initial reserves cannot be uniquely determined from the reservoir past performance. When W,(t) is known, the determination of G from

By D. M. Kehn

A method has been devloped for chromatographic analysis Of the vapor and liquid phases Of a a system containing methane to components having 20 or more carbon atoms. The method uses a windowed equilibrium cell in which volumetric phase behavior of the system can be observed accurately and from which small samples of gas or liquid can be withdrawn for analysis. Analyses are made using two chromatographs, one for the lighter and one for the heavier components in a sample. Combination of the two analyses yields a detailed analysis of the gas or liquid sample. The complexity of the condensate heavy ends is evident from the chromatograms of these fractions, and the predominance of the paraffin hydrocarborn serves as a useful marker in interpreting the chromatograms. The K-values obtained in this analytical method are presented for a high-pressure condensate system and predict closely the observed volumetric behavior of the system. INTRODUCTION Quantitative analysis of hydrocarbons from natural gas reservoirs is necessary for several reasons—to calculate the amount of sales gas produced, to calculate the amount of natural gasoline produced, to plan a liquid recovery system, or to calculate the potential economic value of a reservoir produced under one or more of several different conditions. Analysis of natural gas fluids produced to the surface consists of identifying and computing the mol fraction of each component of the mixture. Although methane is the predominant component, varying amounts of ethane, propane, butane, pentanes and heavier components are also present. Materials containing up to 30 carbon atoms occur in amounts which decrease with increasing molecular weight. However, the quantities of components in the 20 to 30 carbon atom range are usually so small that their importance is negligible, and they are undetect-able in natural gas by ordinary analytical methods. All the components up to those having 20 carbon atoms may sigsficantly affect phase behavior, however. Commonly, only the methane-through-pentane fraction is analyzed quantitatively for each component, while components heavier than Pentane are lumped and repored as "hexane- plus". Expensive, tedious techniques are required for analysis of this fraction. Consequently the detailed analyses needed for prediction of reservoir behavior are usually undertaken only when major gas fields are being developed. The need for complete analyses of condensate systems is apparent when it is recalled that most gas fields are produced by pressure depletion. As the pressure declines, some of the heavier hydrocarbons are lost as liquids which are in the reservoir. In many instances the amount of liquid in equilibrium with the gas phase at high pressure constitutes only 1 or 2 mol per cent of the total system. Flash calculations generally must predict the actual amount of liquid with an accuracy of a few per cent in order to be useful. This retrograde condensation has been understood for years, but accurate correlation methods to permit quantitative prediction of phase behavior in the retrograde region are not presently available. The increasing importance of natural gas has made accurate prediction of phase behavior and composition of produced natural gas streams an economic necessity. The work reported here was undertaken to provide a rapid, economical method for obtaining the vapor-liquid equilibrium information needed to predict accurately the composition of the fluids produced from a gas reservoir throughout its life. TO develop this method, a pressure cell equipped with windows was designed and built for observing the volumes of liquid and gas present at reservoir pressures and temperatures. Use was made of established chromatographic methods for rapid and detailed analysis of both phases. This paper describes the equipment and techniques developed for obtaining vapor-liquid equilibrium data, presents the results of analyses of a condensate system, and indicates the usefulness of these data in predicting hydrocarbon phase behavior. DESCRIPTION OF EQUIPMENT USED The equipment used in obtaining the required information on phase behavior and the complete analysis of hydrocarbon mixtures through C, will be described first, followed by a discussion of the operation of the equipment. It will be helpful, however, to consider first a brief outline of the technique used. A sample of separator gas and liquid is charged to the windowed cell (see Figs. 1 and 2) where volumetric equilibrium phase behavior at reservoir pressures and temperatures can be determined. Then samples of the coexisting phases are withdrawn. The methane-through-pentane fraction is analyzed with a chromatograph equipped with a hot-wire detector, and the pentane-plus fraction is analyzed with a second chromatograph equipped

Jan 1, 1965

By J. H. Hollomon, L. D. Jaffe

The hardenability concept has become widely used during the last few years for the choice and substitution of steels. Before the work of Grossmann,1 the systems for predicting hardenability from chemical composition could be used only over a narrow range of composition. Grossmann introduced a comprehensive system, which has been effective in calculating the hardenability of most types of moderate or low-alloy steels. However, occasions often arise that require the calculation of the hardenability of high-alloy steels from their chemical compositions. Experimental determinations of the hardenabilities of such steels indicate that the Grossmann system predicts much greater hardenabilities than are realized. The fact that cases do arise in which the Grossmann method does not apply indicates that the fundamental hypothesis of the system may not be generally applicable. It seems advisable to re-examine not only Grossmann's system but also the concept of hardenability itself. Hardenability If steel parts are to possess a martensitic structure after quenching, they must first be austenitized and then cooled through the pearlite and bainite transformation ranges sufficiently rapidly to avoid the formation of pearlite, bainite, and pro-eutectoid products.* If, on cooling, these transformations are avoided, the resulting structure can consist only of martensite (and retained austenite). The hardenability of a steel is measured in terms of the severity of the cooling conditions necessary to avoid the pearlite and bainite transformations. The less rapid is the cooling necessary to prevent the formation of bainite and pearlite, the higher is the hardenability. The pearlite and bainite reactions appear to be differently affected by the alloying elements. Not only is this indicated by the published isothermal transformation data, but recent work by Zener2 affords a rational interpretation of the differing effects of the alloying elements. Manganese,3 for example, appears to decrease the rates of the pearlite and bainite transformations by equal percentages, while molybdenum45 is approximately 10,000 times more effective in retarding the pearlite than in retarding the bainite transformation, on the basis of isothermal measurements. In some steels, the formation of bainite restricts the formation of martensite while

Jan 1, 1947

By L. D. Jaffe, J. H. Hollomon

The hardenability concept has become widely used during the last few years for the choice and substitution of steels. Before the work of Grossmann,1 the systems for predicting hardenability from chemical composition could be used only over a narrow range of composition. Grossmann introduced a comprehensive system, which has been effective in calculating the hardenability of most types of moderate or low-alloy steels. However, occasions often arise that require the calculation of the hardenability of high-alloy steels from their chemical compositions. Experimental determinations of the hardenabilities of such steels indicate that the Grossmann system predicts much greater hardenabilities than are realized. The fact that cases do arise in which the Grossmann method does not apply indicates that the fundamental hypothesis of the system may not be generally applicable. It seems advisable to re-examine not only Grossmann's system but also the concept of hardenability itself. Hardenability If steel parts are to possess a martensitic structure after quenching, they must first be austenitized and then cooled through the pearlite and bainite transformation ranges sufficiently rapidly to avoid the formation of pearlite, bainite, and pro-eutectoid products.* If, on cooling, these transformations are avoided, the resulting structure can consist only of martensite (and retained austenite). The hardenability of a steel is measured in terms of the severity of the cooling conditions necessary to avoid the pearlite and bainite transformations. The less rapid is the cooling necessary to prevent the formation of bainite and pearlite, the higher is the hardenability. The pearlite and bainite reactions appear to be differently affected by the alloying elements. Not only is this indicated by the published isothermal transformation data, but recent work by Zener2 affords a rational interpretation of the differing effects of the alloying elements. Manganese,3 for example, appears to decrease the rates of the pearlite and bainite transformations by equal percentages, while molybdenum45 is approximately 10,000 times more effective in retarding the pearlite than in retarding the bainite transformation, on the basis of isothermal measurements. In some steels, the formation of bainite restricts the formation of martensite while

Jan 1, 1947

By Kenelm C. Appleyard

In introducing to an American audience a description of the work done in dry coal separation in England and in Europe generally, it is perhaps desirable to give a short history of the development outside the United States of the particular processes with which the author is connected, and perhaps to stress a little the differences in the nature of the conditions to be faced. England actually presents one set of problems and the Continent of Europe another, since the character of the coals to be treated is entirely dissimilar, and the attitude of the coal industries towards coal preparation is also dissimilar. England for generations has been working by hand good seams of clean coal of the highest possible quality and has not felt any pressing need to clean its coal. Most Continental countries, however, especially in Central and Western Europe, have been working friable and often very dirty coals for so long that a washery is accepted as a part of the normal equipment of a colliery, with the result that the art of wet washing has reached a high state of perfection, particularly in Belgium and Germany. The advent of machine mining has intensified the problems to be faced in all countries, and in England has been coupled with the working out of the best seams in the older coal fields, thus bringing about the necessity of working thinner and dirtier seams with resultant difficulties as regards marketing the products, while Poland, with clean and well prepared coal, has in recent years been attacking established British markets in Scandinavia. In recent years, therefore, interest in coal preparation has been steadily gaining ground in England, although it has not yet reached Continental dimensions. Broadly speaking, the differences in preparation problems between England and the Continent boil themselves down to one of size. In England, for example, with the exception of the Kent coal field, the proportion of coal of a size less than ? in. to the coal less than 2 in. is very much less than on the Continent, and since the principal difficulties in dry cleaning lie in the fines it is easier to produce good figures on

Jan 1, 1931

By H. M. Day

THE constitution of the system silver-mercury has attracted the attention of many investigators during the last two decades, but since their results are for the most part in poor agreement, there is little need for a review of their individual contributions. It remained for the very careful thermal and microscopic investigation of Murphy1 in 1931 to give the constitutional diagram in its present and unquestioned form, which is shown in Fig. 1. He devised methods for taking cooling curves on alloys under high pressures and for the microscopic observation of alloys which contained liquid mercury as a structural constituent at ordinary temperatures. The compositions of the intermediate phases were con-firmed and supplemented through X-ray analyses by Preston and Stenbeck.3 According to Murphy, at 276° C. silver is able to dissolve 44 to 45 weight per cent of mercury, which may increase at lower tempera-tures to about 50 per cent. Preston concluded that the saturation boundary occurred at 46 ± 2 per cent at 100° C. From the values reported in the literature, these are the only ones that may be accepted as lying even in the right region.

Jan 1, 1938

By Y. H. Liu, G. W. Powell

Thin foils made from the gold-rich region of- short (0.15 mm)Au-Ag diffusion couples annealed at 880°C for 1 hr were examined in ax electron microscope and the structures were compared with that of pure gold subjected to identical heat treatments. The couples underwent Plastic deformation (bending) during the diffusional anneal. The foils prepared from the diffusion zone have a higher dislocation density and incidence of subboundaries than pure gold. The plastic bending of the couple can be interpreted in terms of the climb of edge dislocations, which are pavallel to the bend axis, along the direction of diffusion. THE interaction of lattice defects during interdiffu-sion between two metals has been considered by several investigators. In particular, da Silva and Mehl,1 Barnes,' and Bardeen and Herring3 have proposed models based on interactions between point and line defects to account for the Kirkendall effect (marker movement). Each of these models is based on dislocation climb, which can either add or remove lattice planes, induced by an under- or supersaturation of vacancies. A theoretical treatment of the nucleation and growth of voids by the condensation of vacancies has been presented by Seitz.4 Stresses can arise in a binary diffusion couple as a result of the vacancy flux and the gradient in the lattice parameter. rinkmman' has investigated the effects of diffusion-induced stresses on void formation; the results of his analysis suggest that voids can form and grow under the influence of these stresses in the absence of an excess vacancy concentration. The relationships between vacancy supersaturation and diffusion-induced stresses and void formation have been elucidated also by Balluffi and seigle6 who concluded that the stress generated by a vacancy supersaturation aids the growth of voids. Experimental evidence which indirectly shows that stresses are produced by chemical diffusion has been obtained by several researchers.2,7-9 This evidence consists in part of the observation by light microscopy of the formation of subgrains, a process characteristic of the high-temperature deformation of some metals during creep.'0 More striking, however, is the plastic bending of short (0.2 mm) Cu-Ni couples observed by Barnes2 and of boron-doped silicon crystals reported by Queisser.9 Diffusion-induced dislocations in iron and silicon have been investigated by Ainslie et a1.11and Schwutte and Queisser,12 respectively, the former using transmission electron microscopy and the latter an X-ray transmission technique. Matthews and Crawford13 observed the formation of boundaries by the climb of interfacial misfit dislocations in thin, vapor-deposited Au-Pd couples diffused in situ in an electron microscope. In order to obtain additional information on the phenomena associated with defect interaction and diffusion-induced stresses in binary couples, an electron transmission study of foils prepared from the diffusion zone of short Au-Ag couples was undertaken. The initial objective was to investigate the processes occurring at various points of the diffusion zone. Subsequent research demonstrated that foils could be prepared only from the gold-rich region of the diffusion zone using the technique described herein. EXPERIMENTAL PROCEDURE Preparation and Annealing of the Diffusion Couples. The couples were made from annealed, high-purity (99.999 pct). polycrvstalline gold and silver sheets (0.075 mm thick). Shall (0.075 by 5 by 17 mm) elec-tropolished coupons of gold and silver were pressure-bonded by heating the two metals in a graphite device to 770°C and holding at this temperature for approximately 30 min. The quality of the bond was ascertained by metallographic examination at 150 times. Each couple subsequently was annealed at 880°C for 1hr; under these conditions, the extreme portions of the

Jan 1, 1968

By N. Brown

From the theories of flow and fracture it is shown that the difference in reciprocals of the transition temperatures (OK) is a quantitative measure of temper ernbrittlement. Experimental data are given which support this conclusion. STUDIES of temper embrittlement have been made with various viewpoints; some involved a study of the kinetics of the reaction,',2'" others were concerned with changes in the mechanical properties," . and still others investigated the structural differences between the embrittled and unembrittled states by means of the microscope," -ray ,' measurements of electrode potential," and electrical resistivity." In all these studies, the difference in impact properties was the criterion for distinguishing between the embrittled and unembrittled states. By common agreement the difference in transition temperatures is now taken as a measure of the degree of embrittlement, and this measure is used as the quantitative measure upon which studies of the phenomenon are based. Vidal and Jolivet"' suggested that the degree of embrittlement was the same whether measured by impact or by a slow bend test. Their conclusion was based on tests at constant temperature. Jaffe and Buffum" using the impact and slow bend test showed that, for a given degree of embrittlement, the difference in transition temperatures varied with the method of testing. Hultgren and Chang" showed that the difference in transition temperature produced by the V-notched Charpy impact test was not the same as the value produced by the keyhole-notched impact test. This is a very fundamental point because there can be no true measure of temper embrittlement unless it is invariant with respect to the test method. Theory The purpose of this analysis is to show how the transition temperature depends on the stress distribution and the state of the material. The criterion for fracture may be stated as follws: where iF is some function of the principle stresses and F is a critical condition depending on the state of the metal. Similarly yielding occurs when Where is another function of the prin-ciple stresses and Y is a critical value depending on the state of the material. There is some controversy as to the exact form of the function f,.(u,, u,, us) but most experimental data give the following criterion:= where 8, and 6, = 21 or 0. Combinations of 6, and 8, give the various criteria such as the normal stress, the hydrostatic tension, and the maximum shear stress laws. Agreement is general that the octahedral shear stress law adequately describes the yield condition. where the bracketed factor will be called the design factor and depends on the stress distribution. Whether the metal decides to yield or fracture is given by the condition that The effect of temperature and strain rate upon Y has been studied by various investigators, It has been shown by MacGregor and Fisher" that

Jan 1, 1955

By Blake M. Caldwell, Harrold D. Owen

The continued use of permanent-type, we11 completion Iras pointed LIP the need for more powerful through-tubing perforating equipment. A new expendable shaped charge perforator has been developed in which the charges are run through the tubing in a vertical position and then opened out to a horizontal position when at the desired shooting zone. The performance of this new tool is comparable to that of conventional casing type perforators. This paper describes the new tool and its applications. Performance data in targets rind under various actual well conditions are presented. INTRODUCTION The general acceptance and increasing use of pernianent-type well completion by the oil industry has indicated the need for through-tubing perforating equipment with performance comparable to that of conventional casing type perforators.'.' To achieve the performance desired, a new, expendable, shaped charge perforator has been developed with adequate power for effectively perforating both 51/2-in. and 7-in. casing below tubing. This has been accomplished without resulting severe damage to the casing and can he obtained under extremes of pressure and temperature. The design of this new tool is a radical departure from previous concepts of tubing guns since it was felt that the two major limitations imposed by previous designs severely handicapped performance. The first of these limitations was the restriction imposed upon the length of the charges by the necessary small inside diameter of the carrier. This resulted from the necessity for compromises in designing a hermetically sealed gun small enough to allow free passage through 2-in. tubing, yet with sufficient wall thickness to withstand some minimum pressure. In an effort to overcome this limitation, the charges were in some cases placed at an angle with the axis of the well with resulting loss in effective depth of penetration. The second limitation concerned the extreme distance of the charges from the casing when the gun was fired. An example of the latter situation is demonstrated by the fact that a conventional 13/4-in. tubing gun centralized in 51/2-in., 17-lb casing has a clearance of more than 1-9/16-in. on all sides. This means that a considerable portion of the force from each charge must be expended in penetrating this 1-9/16-in. of well fluid before it even reaches the casing. With the gun centered in 7-in., 23-lb casing, the amount of fluid penetration required of each jet is in excess of 21/4-in. In a situation where the 13/4-in. gun is touching one side of the 51/2-in., 17-lb casing, the jets from the charges on the opposite side have more than 3%-in. of fluid to penetrate. A similar situation in 7-in., 23-lb casing necessitates the penetration of more than 4-9/16-in. of fluid. The penetrating effect of the charges is severely impaired in passing through so much fluid. Under such conditions, there is usually insufficient force left to penetrate the casing. Previous studies have shown the decided disadvantage of having to shoot through such an excessive quantity of well fluid.'.' The problem. then, was how to position large powerful charges close to the casing prior to firing and still manage free passage through 2-in, tubing. The solution appeared to be in some method of folding sealed charge units in an open type, expendable. 13/4-in. carrier for travel through the tubing, and unfolding them upon their arrival at the shooting zone in the casing. It was desired to control the mechanism electrically from the surface through the regular shooting cable, making the release of the charges independent of the physical characteristics of the well, yet with a provision to prevent the gun from firing until the

Jan 1, 1955

By L. E. Mannion

Sodium carbonate (soda ash) is one of two principal commercial alkalis. Its principal competitor is sodium hydroxide. The use of sodium carbonate is recorded in ancient Egypt, where naturally occurring brines and solid salts provided impure soda for early glassmaking. Until the 19th century, soda ash (as well as potash) was recovered mainly by leaching wood or other plant ashes. In 18th-century Europe, for example, leaching seaweed ash with hot water produced a brown laundry lye. One of the better grades of this material was a Spanish product, barilla, which analyzed 24 to 30% Na2CO3 (Hou, 1942). The modern chemical industry was born in 1691 with the LeBlanc process for making sodium carbonate from salt, sulfuric acid, and lime. English industry used this process extensively in the 17th and 18th centuries. The next major advance was in 1863, when Ernst Solvay devised the ammonia-soda, or Solvay process. The first of many Solvay plants was built in 1874. These supplanted the LeBlanc method and dominated worldwide soda ash production until 1974, when mined sodium carbonate became predominant. Although considerably less important until recently, natural sodium carbonate deposits historically have supported small soda ash operations throughout the world. Shortages during World War II stimulated production of "natural" soda ash from such deposits, particularly at Searles Lake, CA and Lake Magadi, Kenya. More spectacularly, increased production from the vast trona deposits in Wyoming has virtually supplanted the Solvay process in the US. Principal producers of natural soda ash as well as the character of the source deposits are listed in Table 1. [ ]

Jan 1, 1983

By E. R. Parker, C. F. Riisness

That grain size has a great effect on the mechanical properties of metals has been recognized for a long time. Bassett and Davis1 in 1919 did excellent work in determining the effect of grain size on the hardness of brass. About the same time Jeffries2 and Sykes3 ascertained the effect of grain size on the strength and ductility of several metals at temperatures ranging from 80°K. to their melting points. When creep was recognized as an important property of metals, those engaged in the study of this property tried to determine the effect of grain size4-9 on creep rates. Unfortunately, most of the investigations were conducted on only two grain sizes, often designated simply as "fine" and "coarse." It is well known that at high temperatures coarse-grained test bars creep less than fine-grained bars. The relation between grain size and size of test bar, however, has been frequently overlooked. In his early work, Jeffries2 showed that the number of grains in the cross section has a more important influence on the properties of the material than the actual grain size. More recently Hanson and Sandfordl0 and Pell-Walpole,ll in their measurements of the creep and tensile properties of tin, tested a wide range of grain sizes and correlated the grain size with the strength. Hanson9 later established the relation between the number of grains in the cross section and the creep rate. At high temperatures, generally a coarsegrained structure is considered superior in creep to a fine-grained structure, but it is evident that for a given bar size continuously increasing the grain size will

Jan 1, 1944

By C. F. Riisness, E. R. Parker

That grain size has a great effect on the mechanical properties of metals has been recognized for a long time. Bassett and Davis1 in 1919 did excellent work in determining the effect of grain size on the hardness of brass. About the same time Jeffries2 and Sykes3 ascertained the effect of grain size on the strength and ductility of several metals at temperatures ranging from 80°K. to their melting points. When creep was recognized as an important property of metals, those engaged in the study of this property tried to determine the effect of grain size4-9 on creep rates. Unfortunately, most of the investigations were conducted on only two grain sizes, often designated simply as "fine" and "coarse." It is well known that at high temperatures coarse-grained test bars creep less than fine-grained bars. The relation between grain size and size of test bar, however, has been frequently overlooked. In his early work, Jeffries2 showed that the number of grains in the cross section has a more important influence on the properties of the material than the actual grain size. More recently Hanson and Sandfordl0 and Pell-Walpole,ll in their measurements of the creep and tensile properties of tin, tested a wide range of grain sizes and correlated the grain size with the strength. Hanson9 later established the relation between the number of grains in the cross section and the creep rate. At high temperatures, generally a coarsegrained structure is considered superior in creep to a fine-grained structure, but it is evident that for a given bar size continuously increasing the grain size will

Jan 1, 1944

By Frank W. Osterwald

Violent, spontaneous destruction of coal faces and ribs during, what are commonly called, bumps endangers and at times destroys life and property in mines of the Book Cliffs coalfield, Carbon County, Utah. Because these mines supply much of the coking coal for the West Coast steel industries, mining is necessary, although costs are high and operating conditions are very difficult at times. As operations continue, mining will go to greater depths, and the difficulties will increase. Whether or not mining can be continued successfully depends in part on whether or not incidence of bumps can be controlled successfully. For this reason, the U.S. Geological Survey, at the request of and in cooperation with the U.S. Bureau of Mines, undertook a study of the Sunnyside No. 1 mine to determine what geologic factors were related to the incidence of bumps. This report presents the preliminary results of that study and indicates that some observable geologic features in the mine may be related directly or indirectly to bumps, and that other features may be used to infer stress distribution around workings that will aid in design of roof support measures. Coal is mined in the Sunnyside No. 1 mine from depths as great as 2500 ft by room-and-pillar methods. The surface topography is rugged with many steep cliffs and deep canyons, hence the load on the coal varies greatly within short distances. Much of the Sunnyside coal is under high stress, and while being mined, it shatters continuously' and falls from the face. Continuous shattering (bumping) makes mining easy, but if the shattering is interrupted, greater stress is built up and violent bumps may result when the coal is mined.

Jan 4, 1962

By E. H. Tenney

A discussion of the probable future use of coal for power development involves the study of several basic factors, such as future demand for power, the quantity and availability of fuels in direct competition with coal, the price of coal, and a closely related factor—the efficiency and cost of fuel utilization. Predictions based on purely statistical analyses of past coal consumption have definite limitations. For example, statistics showing the relation between coal utilization and total energy consumption from all sources between the years 1890 to 1930 indicate that during that period the energy consumption per person in the United States increased five times, while the coal consumption per person increased only twice1, and there has been an actual decrease in per capita coal consumption since 1920. Figures such as these, compiled by authentic agencies, emphasize the need for caution in attempting estimates as to the future use of coal, and, incidentally, would seem to offer little basis for optimism in the coal industry. They also suggest the value of analyzing broadly the part played in the past by the related factors of power consumption, competitive fuels, coal prices and the efficiency of utilization. Proper weight must also be given in such a study to the present status and limitations of power-plant developments, arid to the question of what the coal industry itself can do to further its own interests arid influence the consumption of its product.

Jan 1, 1936

By E. H. Tenney

A discussion of the probable future use of coal for power development involves the study of several basic factors, such as future demand for power, the quantity and availability of fuels in direct competition with coal, the price of coal, and a closely related factor—the efficiency and cost of fuel utilization. Predictions based on purely statistical analyses of past coal consumption have definite limitations. For example, statistics showing the relation between coal utilization and total energy consumption from all sources between the years 1890 to 1930 indicate that during that period the energy consumption per person in the United States increased five times, while the coal consumption per person increased only twice1, and there has been an actual decrease in per capita coal consumption since 1920. Figures such as these, compiled by authentic agencies, emphasize the need for caution in attempting estimates as to the future use of coal, and, incidentally, would seem to offer little basis for optimism in the coal industry. They also suggest the value of analyzing broadly the part played in the past by the related factors of power consumption, competitive fuels, coal prices and the efficiency of utilization. Proper weight must also be given in such a study to the present status and limitations of power-plant developments, arid to the question of what the coal industry itself can do to further its own interests arid influence the consumption of its product.

Jan 1, 1936