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By Shueling Woo, Charles S. Barrett, Robert F. Mehl

When one solid phase is generated from another, fixed and rational orientation relationships are observed to subsist between the parent and the new crystal. The principle has been proposed1 that the relationships obtaining between the same two phases are identical whatever the type of phase change involved, or whichever of the phases may act as parent. Many types of phase changes have been studied: allotropic transformations in pure metals, precipitation from solid solutions, eutectoid decompositions, peritectic reactions, the formation of oxide layers, and others2 Phase layers generated by diffusion of one metal into another constitute an additional type of reaction. This report provides new data on the orientation relationships occurring between phase layers formed by diffusion, in the Cu-Zn system,§ and furnishes further evidence in support of the principle. Materials and Methods The Cu-Zn system is especially suitable for these studies since the high vapor pres- sure of Zn provides an opportunity readily to create one phase poorer in Zn upon a parent phase richer in Zn by removing Zn by vaporization, or to reverse this process by adding Zn from Zn vapor; e.g., the beta phase can be found as a layer upon gamma by dezincing, or gamma can be found on beta by addition of Zn from Zn vapor. Since orientation relationships are to be sought, requiring crystals large enough for orientation determinations, it is convenient to prepare single crystals or large grains of the parent phase. The samples were prepared from oxygen-free high-conductivity copper and Horse Head zinc by melting under a borax flux in a graphite crucible. Large crystals of beta brass were grown by the strain-anneal method, in plates sectioned from the cast ingots, by the following procedure. Rockwell-hardness indents were made at I cm. intervals and with various loads, then the plates were annealed for 4 days at 700°C. in Nichrome boxes packed with beta-brass chips and graphite. Surface layers were removed by grinding and etching to a depth of about 1.0 mm., and individual grains were cut out. Crystals of alpha and gamma brass were prepared by freezing, by lowering a graphite crucible at speeds less than one inch per hour through a furnace held at a constant temperature above the melting point. Single crystals were cut out with a jeweler's saw, ground, polished and etched. Care was taken to remove cold-worked layers from the finished crystals

Jan 1, 1944

By Charles S. Barrett, Robert F. Mehl, Shueling Woo

When one solid phase is generated from another, fixed and rational orientation relationships are observed to subsist between the parent and the new crystal. The principle has been proposed1 that the relationships obtaining between the same two phases are identical whatever the type of phase change involved, or whichever of the phases may act as parent. Many types of phase changes have been studied: allotropic transformations in pure metals, precipitation from solid solutions, eutectoid decompositions, peritectic reactions, the formation of oxide layers, and others2 Phase layers generated by diffusion of one metal into another constitute an additional type of reaction. This report provides new data on the orientation relationships occurring between phase layers formed by diffusion, in the Cu-Zn system,§ and furnishes further evidence in support of the principle. Materials and Methods The Cu-Zn system is especially suitable for these studies since the high vapor pres- sure of Zn provides an opportunity readily to create one phase poorer in Zn upon a parent phase richer in Zn by removing Zn by vaporization, or to reverse this process by adding Zn from Zn vapor; e.g., the beta phase can be found as a layer upon gamma by dezincing, or gamma can be found on beta by addition of Zn from Zn vapor. Since orientation relationships are to be sought, requiring crystals large enough for orientation determinations, it is convenient to prepare single crystals or large grains of the parent phase. The samples were prepared from oxygen-free high-conductivity copper and Horse Head zinc by melting under a borax flux in a graphite crucible. Large crystals of beta brass were grown by the strain-anneal method, in plates sectioned from the cast ingots, by the following procedure. Rockwell-hardness indents were made at I cm. intervals and with various loads, then the plates were annealed for 4 days at 700°C. in Nichrome boxes packed with beta-brass chips and graphite. Surface layers were removed by grinding and etching to a depth of about 1.0 mm., and individual grains were cut out. Crystals of alpha and gamma brass were prepared by freezing, by lowering a graphite crucible at speeds less than one inch per hour through a furnace held at a constant temperature above the melting point. Single crystals were cut out with a jeweler's saw, ground, polished and etched. Care was taken to remove cold-worked layers from the finished crystals

Jan 1, 1944

By H. M. Davis, T. S. Jones

A methodfor accelerating the reduction of a metal oxide by carbon monoxide is to incorporate in the reduction system a nonreducible oxide which has a strong affinity for carbon dioxide and will remove it from the product gases. The effectiveness of this method was investigated by veduction experiments on specially prepared powder mixtures of SrO-ZnO ("active'.) and SrCO3-ZnO (reference). Measurements at 750o and 677°C showed that the rate of reduction of ZnO by CO was as much as an order of magnitude greater in the presence of SrO. Under the experimental conditions at least as much CO2 as generated by veduction was absorbed when SrO was present. Enlzancernent of the veduction rate by SvO resulted from modification of' gaseous djfitsion processes. THE specific question posed in this investigation was whether the reduction reaction CO + ZnO - Zn(g) + COa [1] could be accelerated by incorporating strontium oxide into the oxide charge undergoing reduction. Provided the strontium oxide was active enough, it could remove carbon dioxide from the product gases of ( 11 and form strontium carbonate, thus modifying Reaction [ 1] to CO + ZnO + SrO = Zn(g) + SrCO3 [ 2] This study of the comparative rates of Reactions [ I] and [2] can be considered as a particular case of a general scheme for increasing the rates of reduction of metal oxides by carbon monoxide. The limits of applicability of this scheme are indicated in the simple thermodynamic analysis presented in the appendix. This analysis primarily dictated the choice of the system, CO-ZnO-SrO, employed in this investigation. In addition, it was thought that a study of this scheme by use of the CO-ZnO-SrO reaction system would be of special interest in view of indications in the literature1-3 that the gaseous reduction of zinc oxide is prone to rate control by diffusion in the gas phase. The distinction should be pointed out between this and other efforts to increase the rates of reduction reactions through the use of addition agents. Additions of a wide range of chemicals have been tried with de- grees of apparent success varying from slightly negative to highly positive. The reasons for making additions have included the use of salts to produce effects akin to catalysis,4, 5 the alteration of the microstruc-tural details of the reduction process (including solid-state diffusion),6-8 and the conversion of an en-dothermic reaction into one that is exothermic or autogenous.9-12 The means used to attempt alteration of the enthalpy change has commonly been to incorporate lime into the charge, so that heat is generated by reaction with either of the reaction products, carbon dioxide or water. The use of lime in this way makes endeavors such as that of Edstrom and Wiberg similar to the present one. Furthermore, the basic principle behind the present work has previously been set forth.13 However, a detailed investigation of the type of reaction described in this work does not appear to have been conducted. EXPERIMENTAL PROCEDURE From both conceptual and physical standpoints, Reaction [2] is to be considered as the sum of two reactions:

Jan 1, 1968

By C. P. Mangelsdorf

The roof truss as a means of secondary or supplemental mine roof support has enjoyed increasing acceptance in recent years, particularly in bituminous coal mines. In those entries where long life is required or doubtful performance from other forms of support seems likely, trusses in many cases have provided the necessary protection for continuing operations. Although relatively expensive and time-consuming in their installation, trusses, particularly with the new resin point anchor system, appear to be justifying their higher premium. It seems inevitable that techniques and equipment for installing them within the cycle will soon be developed. The actual mechanism by which trusses contribute to the stability of a roof is, as yet, poorly understood, and it may be that more than a single mechanism is involved. There are, however, a number of useful observations which can be made concerning the structural behavior of the truss itself, based solely on the mechanics of rigid and deformable bodies. The purpose of this article is to present some of these observations, particularly relating to friction in the system. A few speculations concerning the roof must, of course, be made. From a knowledge of the structural behavior, some insight into the truss-roof interaction may be gained. The concept of the truss is quite simple. As shown in [Fig. 1], it consists of two inclined chords (usually at 45') anchored in holes drilled in the roof over the ribs. A horizontal chord is formed connecting the exposed ends of the inclined chords, either with a third piece or by bending extensions of the inclined chords until they meet in the middle. A distinction can be made between active and passive chords of a truss depending upon the manner of installation. If the inclined chords are fully grouted and the horizontal chord is merely attached to them, it may reasonably be assumed that no significant forces exist in the truss until the roof begins to work. Such would be a completely passive system. On the other hand, if the inclined chords are anchored only at their upper extremities and the horizontal chord is formed in such a way that all three chords can be pretensioned to a significant portion of their tensile strengths then the truss may be regarded as fully active. Combinations of active and passive chords are also possible. * The discussion here is confined to the fully active truss such as the Birmingham steel rod system or the Galis wire rope truss. In both cases, pretensioning is accomplished by tightening of the horizontal chord, some of which tension is transferred to the in-

Jan 1, 1981

By George A. Roberts

The development of an alloy system, high-speed steel, is used as an example of the progress of physical metallurgy. Tracing the history of men and their thoughts as they studied and invented and modified these materials, the story of high-speed steel since the 1890's is seen to be a long, slow, but steady progression of achievements. Today's multiplicity of high-speed steels are the result. Data are presented on quantitative metallography of carbides in high-speed steel with high vanadium content using the QTM instrument. Grindability as well as mechanical properties are related to the content of excess MC and M6C carbides in a series of high-speed steels and the newer matrix steels. These emphasize the present state of knowledge and show the current stages of thought that may affect the development in succeeding years. It is a great thrill for me, an ex-research metallurgist and ex-practicing metallurgical engineer, to speak to an audience currently engaged in both pursuits on the occasion of the 43rd Howe Memorial Lecture before the Iron and Steel Division of the AIME. I shall not review Henry Marion Howe's distinguished career, so adequately reviewed in Maxwell Gensamer's contribution in the 1965 AIME History of Metallurgy, except to point out that, while leading the life of an intellectual, he worked as a practicing research metallurgist and a practicing metallurgical engineer for significant periods of time and contributed greatly in both areas. For those of you who believe, as I do, that in the intellectual activity of metallurgy we are blessed with an intimate mixture of science and engineering (see Mehl's 1960 Howe Lecture), we might recall that Howe, while pursuing a life of writing and teaching in later years, served as the first Chairman of the Division of Engineering of the National Academy of Sciences. That metallurgists were called upon then to lead an engineering recognition movement is perhaps related to the strong part played by the AIME and its members in the recent establishment of a National Academy of Engineering and to the fact that a metallurgist is its head, 47 years after Howe served. I stress these engineering aspects for I wish to talk about a metallurgical engineering subject today. Alloy systems, physical metallurgy, and steel blended with an historical perspective and a report on new techniques to improve the old will, I trust, be of sufficient interest to bring these lectures back to the physical-metallurgy banner from which they have departed for 4 years. Those process metallurgists, open-hearth fiends, and physical chemists among you will just have to be patient. The development of an alloy system is the engineering application of scientific thought and fact. There are many interesting alloy systems, developed to a high degree of technology and sophistication over the past 40 to 70 years. These systems are bound together and related by a similar set of characteristics. For example, stainless steels are a system in which the members are related by a high chromium content which gives a corrosion-resistant characteristic. A subfamily in this system would be austenitic steels

Jan 1, 1967

By D. L. Garthwaite, F. M. Stewart, F. K. Krebill

Pressure has been maintained in the Elk Basin Ten-deep reservoir since the initiation of inert gas injection in Sept., 1949. Oil is being produced under conditions favorable for gravity drainage, including high angle of dip, appreciable structural closure, and fairly good per~neability. Results being obtained are high per cent recovery of oil-in-place, sustained field productivity, reduced operating problems, and recovery of plant products. The high recovery has been calculated by alpplication of the gravity drainage theory described in an earlier AIME paper.' It is also confirmed from field performance by comparing nil recovery to date with gas cap spuce voided. GENERAL INFORMATION The Elk Basin field lies in Park County, Wyo., and Carbon County, Mont., approximately 50 miles east of Yellowstone Park. Located at the northern end of the Big Horn Basin. the field is situated on an elongated asymmetrical anticline (Fig. 1). The pressure maintenance project covered by this paper involves the Embar-Tensleep reservoir in this multi-pay field. Discovered in Nov., 1942, it has a proved productive area of over 6,300 acres. It consists of the 210-ft thick Tensleep sandstone of Pennsylvanian Age overlain by 40 ft of Embar dolomite of Permian Age. The two formations apparently are in communication with each other and are produced as a common source of supply. As 98 per cent of the reserves are contained in the Tensleep sandFtone, in this paper the Embar-Tensleep reservoir will he called simply the Tensleep. The reservoir is found at an average depth of 4,900 it, is approximately 7 miles long and 2 miles wide, and has a maximum oil productive closure of 2,330 ft. The strata dip an average of 21" on the west flank and 45" on the east. There are presently 132 Tensleep wells in the field drilled on 40-acre spacing; of these, 17 are shut in because of high gas-oil ratio (GOR) and eight are gas injection wells. Rock characteristics and related information for the pay section follow: Porosity, avg 10.7 per cent Permeability (air) from cores, avg 118 mds Permeability from PI'S 91 mds Connate water, avg 8 per cent Initial pressure (-400 ft) 2,234 psia Pressure April 1954 (-400 ft) 1.327 psia At high structural positions much of the better sandstone has connate water content of only 2 to 5 per cent as indicated by the coring of wells with oil in nearby Tensleep fields. In special imbibition tests, samples readily imbibed oil but repelled water. In tests on crushed samples, the sand grains rapidly settled in oil and carbon tetrachloride but formed a stable unsinking floc in water. This information indicates that the Tensleep sand is preferentially oil wet. The oil produced averages 29' API gravity and has a high sulfur content. Extensive sampling and testing have established the fact that characteristics of reservoir oil in this field vary greatly with structure, see Fig. 2. Additional detail on the variation of oil characteristics with structure at Elk Basin may be found in Reference 2. At original reservoir pressure the oil was undersatu-rated with gas, the bubble point being 1,250 psi at the crest but only 500 psi at the lowest elevation sampled. As noted on Fig. 2, other fluid properties—reservoir volume factor. solution ratio, gravity, viscosity, and hydrogen sulfide content—likewise vary greatly. These variations complicate mathematical analysis, for it is necessary to average these characteristics in order to enter them into reservoir engineering expressions. To further complicate analysis, sand-face pressure also varies greatly because of the increase in fluid head down structure. As an approximation, average properties under initial conditions may be read from Fig. 2 at the -450-ft elevation.

Jan 1, 1956

By H. K. Shearer

Oil production in north Louisiana in 1937 was 28,668,070 bbl., an increase of 1,896,925 bbl., or 7.1 per cent over 1936, as against an increase of 178 per cent from 1935 to 1936. Gas production of 301,148 million cu. ft. from gas wells and 17,330 million cu. ft. of casinghead gas, a total of 318,483 million, was an increase of 33,483 million cu. ft., or 11.7 per cent over 1936. Well completions numbered 716, with 411 oil wells, 175 gas wells and 130 dry holes; compared with 346, 109 and 78, respectively, in 1936. There were 58 wildcat dry holes. In addition to the wildcat producers described and tabulated with the fields, there were two small, shallow gas wells in Sabine and Tensas Parishes, which did not open fields of any present importance. At the close of 1937 there were only five wildcat tests actually drilling, with nine others shut down or temporarily abandoned. Chief interest during 1937 was in development rather than discoveries. The only real discoveries were two deep gas and distillate fields, Bear Creek and Ruston. There were also three completions of gas-distillate producers from deeper formations in old fields, of which the most important was at Cotton Valley, one discovery of oil in a previously known gas sand and five or six extensions of some importance. Geological Section The columnar section in south Arkansas (Fig. 1, p. 317) also applies in north Louisiana, with a few changes noted below. The oldest known formation in north Louisiana is a bed of rock salt. Except on salt domes, only one well at Rodessa has been drilled into this salt, but it has been penetrated by a number of wells in south Arkansas. Salt domes have been discovered near Vicksburg and Hattiesburg, Miss., and a deep well in Limestone County, Texas, has drilled into rock salt. In Louisiana the distance between the "interior salt-dome basin" and a salt dome of the "Gulf Coast salt basin" is hardly 60 miles. In short, evidence is accumulating to indicate that all of Louisiana, with the possible

Jan 1, 1938

By Arthur H. Wilson

INTRODUCTION The stratified deposits of the coal measures are strongly laminated and exhibit a high degree of anisotropy. The stronger rocks in the sequence possess joints and shear planes, the coal itself has a closely spaced cleat pattern, and the softer rocks are capable of flowage. To calculate the general distribution of stress in such a medium by analytical means based on the theories of elasticity is difficult, and has not yet been satisfactorily achieved. Nevertheless, some estimate is required to aid the design of supporting pillars and permit the correct siting of main roadways. This is important when laying out districts for longwall extraction, particularly if the results of previous experience are not available in the area to be exploited. Although elastic stress analyses, including finite element analysis, may not be very appropriate, the basic equilibrium conditions will apply. These, combined with logical deductions based on observed fact, can be used to give appropriate solutions which experience has shown to be capable of giving acceptable results in the design of pillars associated with longwall workings. Constancy of cover load is one of the fundamental equilibrium conditions. When mining below ground, the cover is not removed, therefore the average vertical load after mining must equal the initial cover load. If mining produces a local decrease in load in any particular area, it must be balanced by an equivalent increase in load nearby. Bending moments in the strata above are capable of compensating for the turning moments which this redistribution of load may produce, and the existence of a "rear abutment", much discussed between 1950 and 1960, is not an essential equilibrium requirement. If the distribution of vertical stress is plotted three-dimensionally, then the load on any small element of area 6S will be o.6S, where o is the average stress. This also represents the volume of the "stress envelope" which lies above 6s. By making the individual areas very small and summing together, it is possible to show that the total load on any particular area can be found by calculating the volume of the stress distribution envelope which lies above it. A similar consideration applies to the stress distribution in a two-dimensional situation. If the stress distribution curve is drawn, then the area below any portion will represent the load per unit depth of section. For example, Figure 1 represents the possible stress distribution across a caved waste and associated ribside. If AW is the load deficiency [ ] These loads must balance, therefore area AW = AS, and if one can be deduced, the other will then be known. Attempts have been made to measure stress distributions in the ribside and in the waste. Stress meters in soft rocks such as the coal measures have not proved very effective. Those based on the measurement of strain have experienced difficulty in strata capable of flowage, high modulus stress meters suffer from cross sensitivity, and overcoming to obtain absolute stress is almost impossible. Load measuring instruments left in the waste have also proved largely ineffective, mainly as a result of the difficulties of protecting the leads in a caving environment. Certain logical deductions, however, can be made about the conditions in the waste. CONDITIONS IN THE WASTE Over the area of the waste the surface trough which develops is remarkably consistent, despite the geological variations which occur from coalfield to coalfield. In Britain, an accuracy of 210% is claimed for subsidence prediction based on width of extraction and depth of cover (National Coal Board, 1975). The subsidence in the USA is more variable (Adamek and Jeran, 1981), particularly with respect to the point of inflexion, but the same general pattern occurs. At the shallower depths the somewhat harder roof strata involved in the caving in the USA may suffer less compaction, giving reduced values of subsidence. Subsidence at intermediate horizons below the surface

Jan 1, 1982

By A. L. Ph. B. Holley

(Read at the Philadelphia Meeting, February, 1878.) THIS paper is an abstract and a discussion of results obtained by the United States Test Board in experiments upon 14 brands of wrought iron, most of which are well known and of high repute.* The iron was all intended for chain-cables; it was tested in the form of bars, usually of nine sizes, from 1 inch to 2 inches round, and also in the forms of single links and short chains. Not less-than 2000 tensile tests were made, each showing elastic limit, elongation, and reduction of area. This work was done with conspicuous intelligence and fidelity, at the Washington Navy Yard, by Commander L. A. Beardslee. Some important practical results and principles which he has developed, and others which he has confirmed, will be referred to. The chemical part of this work consists of 42 complete analyses (including slag), by Mr. Blair, chemist to the Board. EFFECTS OF COMPOSITION ON STRENGTH. Variations in the physical qualities of iron may he due to different composition, or to different treatment in manufacture, or to both these complex causes. In order to determine the specific causes of variation, one class of altering conditions should be made to vary largely, while the other classes should be kept uniform. Then another class should be varied, and so on, until the value of each is ascertained. As all the irons under consideration were intended to have that purity and refinement which was deemed indispensable in chain-cables, their chemical analyses are perhaps more important in proving that physical variations result chiefly from treatment, than in pointing out the specific effects of certain ingredients. While the subject of treatment-especially the increase of strength by greater reduction in rolling-may be the more important one, it can be best appreciated after we have familiarized ourselves with the gen¬eral chemical and physical characters of the irons. The typical facts are given in the following tables. * As the present object of the Board is not to compare the products of different makers, but to discover the physical effects of various composition and treatment, the irons are designated by letters rather than by their trade names.

Jan 1, 1878

By Clarence S. Ross

INTRODUCTION THIS chapter on the rô1e of physical-chemical processes in ore deposition presents unusual difficulties because it attempts to discuss the theory of processes that are very imperfectly under- stood, but which are among the most fundamental problems now before the student of ore formation. It is generally believed that a great variety of ore deposits are in some way derived from igneous rocks; but we desire to know the mechanism of their splitting off from the parent magma, the physical and chemical character of the material that acts as a medium for transfer from magma to the point of deposition, the manner of deposition, and the methods of replacement and removal of the invaded rocks. This problem is difficult for the field geologist because it concerns forces that for the most part have long since ceased to act. It involves a complex system of which the time for completion extends from the first development of the parent magma through its intrusion, its slow cooling and crystallization, and the final escape of its last residuum, a time probably represented by millions of years. In space the processes extend from profound depths of the abyssal magma which can never be directly observed, through the horizons characterizing deep-seated igneous rocks and ore deposits; those formed at moderate depths; and ends with surficial ones and surface thermal springs. The geologist usually can study the effect at but one of these horizons: he must attempt to fit his puzzle together while seeing but a few parts at a time. Thus he must deal with many isolated phenomena, as if they were the result of many physical and chemical systems; when in fact his problem involves a single exceedingly complex system, and will only be understood when that entire complex system is understood. The geophysicist is handicapped because he must attempt to interpret an extraordinary complex system, involving physical and chemical conditions which he can never hope to duplicate fully, through the study of many exceedingly simple systems.

Jan 1, 1933

By B. N. Bose, M. F. Hawk

SINCE Davenport and Bain' introduced the isothermal transformation technique for the study of austenite decomposition in steels, a new field of investigation has opened up. Extensive research has been carried out on many different steels, but relatively little work has been done on eutectoid transformations in analogous alloy systems. The researches of Smith and Lindlief,² Mack,³ and Klier and Grymko²0 on the beta-phase transformation in copper-aluminum alloys, of Hibbard, Eichelrnan, and Saunders4 and Smith5 on the kappa-phase transformation in copper-silicon alloys, of Chaudron and Forester6 on the decomposition of "FeO," and of Wasserman7 on similarities between the iron-carbon, copper-aluminum, copper-tin, and copper-beryllium systems essentially comprise the field. The iron-nitrogen system, in view of its remarkable similarity to the iron-carbon system, is particularly attractive for the study of eutectoid decomposition. The present investigation is concerned with the study of isothermal transformation, proceeding by the familiar nucleation and growth processes, and of martensitic transformation characteristics of pure iron-nitrogen alloys. The kinetics of transformation and the morphology of the transformation products have been investigated, for these must be the factors determining the properties and behavior of the final product. The Iron-Nitrogen System he binary iron-nitrogen phase diagram has been a matter of considerable disagreement among vari01.1s investigators. However, the phase diagram according to Eisenhut and Kaupp8 and Lehrer10 is now considered essentially correct as reproduced in fig. 1. The important values, 2.35 pct nitrogen and 591°C, for the co-ordinates of the eutectoid point (obtained from this diagram and used in the re- search to be described) were confirmed in a concurrent study of Paranjpe, Cohen, Bever and Floe." The eutectoid decomposition involves the transformation of the ? face-centered cubic interstitial solid solution of nitrogen in iron to the a body-centered cubic interstitial solid solution of nitrogen in iron and the ?' nitride of iron. This nitride is essentially the compound Fe,N; it also possesses a face-centered cubic lattice but a considerably larger one than the ?; the nitrogen atoms in ?' are arranged in an ordered way in the centers of the unit cubes.8,10,11 A martensitic structure has also been reported8,12 in iron-nitrogen alloys and was studied in the research to be described here. Materials and Methods The specimens used in this investigation were prepared by nitriding "pure" iron. This iron was supplied by the Westinghouse Research Laboratories and is the product bearing their trade name "Puron"; it contains about 0.04 wt pct total impurities, the major portion of which is oxygen. Specimens were ribbons several inches long, a tenth of an inch wide, and 0.125 mm thick; this was the

Jan 1, 1951

By Anton Sawatzky, Erich Vogt

By means of mathematical solutions to the appropriate diffusion equations, we describe the kinetics of the thermal diffusion of hydrogen in Zircaloy-2 for the various temperatures and concentrations encountered in a heavy water moderated reactor. When the hydrogen concentration is below terminal solid solubility only the a Phase is present. Redistributions are then described in terms of the characteristic functions of the difhsion equation. For higher concentrations both the a and 6 phases are present. We assume the two phases to be always in equilibrium. For moderately small hydrogen concentrations exact solutions of the two-phase equation approach the the approximate solutions derived by Sawatzky and for all concentrations the exact solutions exhibit the qualitative features of his result: the two-phase concentration increases with time, everywhere; in the absence of a hydrogen current at the hot end of the sample an a-phase region always exists there; the interface of the a + 6 , a-phase boundary moves toward the cold md of the sample and the hydrogen concentration is discontinuous at the interface. Simultaneous solulions of the a and a + 6 hydrogen distributims and of the concomitant interface motion are obtained and compared to the observations of Sawatzky and Markowitz. The kinetics of the hydrogen diffusion process are shown to lead to m apparent heat of transport of the a phase which is lower than the actual value (even for samples with long anneals) thus resolving at least partially the disparity between experimental measurements of this quantity. A number of recent papers1"4 have reported measurements on the diffusion and redistribution of hydrogen in Zircaloy-2 under temperature and concentration gradients. These studies were instigated by problems arising from increasing use of Zircaloy-2 as a fuel element cladding material in pressurized-water power-reactors. The Zircaloy-2 picks up hydrogen during the operation of the reactor: the consequent precipitation of zirconium hydride in the Zircaloy-2 has pronounced effects on its mechanical properties. The Purpose of the present Paper is to describe the kinetics of the thermal diffusion of hydrogen in Zircaloy-2 for the various hydrogen concentrations and temperatures likely to be encountered in reactors. When the hydrogen in the Zircaloy-2 is entirely in the solid solution phase (a phase), the differential equation for thermal diffusion is well known and the redistribution can be described by standard mathematical methods some of which are given in Section 11 below. The treatment of the a + 6 (hydride) region differs from the earlier treatment of sawatzky3 by taking into account several modifications of the two-phase diffusion equations as suggested to us by Markowitz4 and Kidson.5 Even with the modifications the results obtained in our more complete treatment are substantially the same as those found by Sawatzky. As we show, the difference between the results of sawatzky3 and kIarkowitz4 is largely due to the difference in the geometry of their experiments. In the next section we derive the modified two-phase equation for arbitrary geometry. The exact solution of this equation is given in Section III for linear and cylindrical geometry. It is shown that Sawatzky's approximate solution is quite accurate for almost all the temperatures and hydrogen concentrations which are actually encountered. In Sawatzky's approximate theory the hydrogen concentration everywhere in the two-phase region increases continuously. As his paper pointed out, this result, together with hydrogen conservation, implies that in a sample with no hydrogen current flowing into the hot end a two-phase region is always accompanied by a single-phase region at the hot end of the sample. The net hydrogen gain in the two-phase region is supplied by the decrease of hydrogen in the single-phase region and by the movement of the (a, a + 6) boundary toward the cold end of the sample. Hydrogen conservation at the (a, a + 6) boundary leads to a discontinuity in the concentration and its derivative there. In Section IV it is shown how these qualitative features of the thermal diffusion kinetics arise from the simultaneous solution of the a-phase differential equation and a + 6 phase equation. Methods derived by us previously for the solution of the redistribution in both phases and the accompanying motion of the boundary are used to obtain approximate solutions valid for large times. The solutions account well for the observed redistributions of Sawatzky and Markowitz. It is shown how the continuing motion of the (a, a + 6) boundary leads to measured values of the heat of transport lower than the actual value, even for specimens with relatively long anneals.

Jan 1, 1963

By Rollin Farmin

Rock pressure against the supports for underground workings in certain mines becomes sufficiently severe to crush sound timbers. The cost of maintenance of these mines increases critically as the workings are extended. "Heavy ground " and "swell-jng ground" are terms commonly applied to a condition of excessive pressure from the wall rock. Defined for the purposes of this paper, "heavy ground" delivers gravi-tative pressure on the supports of a mint opening; "swelling ground" delivers pressure arising from expansion of the wall rock. Mining problems created by heavy ground have been studied extensively by mining engineers, as in the recent Symposium on Block caving.' A parallel study of rock bursts2 attacks the field of ground that ruptures under strain. The problem of swelling ground, which has received less current attention, is the subject of this paper. An ExaMPLe of Swelling Ground Severe cases of swelling ground are found in the gougy shear zones in mines along the western Sierra Nevada, where the veins are accompanied by faults through altered serpentine, schist and slate. For example, along troublesome stretches in the ldaho Maryland mine, Grass Valley, California, swelling ground continues to crush drift timbers, with diminishing intensity, for 3 to 10 years after entry. During this period, from five to nine generations of crushed timber sets must be replaced and a large additional tonnage of scaly rock and wet gouge must be removed from the drift to make room for this succession of new timbers. After "the squeeze has been taken out of the ground" the timbers will stand for years, until they collapse from decay. Heaving of floor and footwall along drifts develops soon after the timber sets are placed and frequent grading down of the track is necessary to keep it serviceable and to maintain headroom. If sills are placed under the drift posts, the sets break more quickly and the track becomes impassable at once. When the floor is left Open? and the bottoms of posts and stulls are pencil-pointed, the scaly ground of the fault zone swells up around the timbers (Fig. I) instead of breaking them (Fig. 2). A foot or two of this encroaching ground is trimmed from the floor and lower sides of the drift several times before complete retimbering is necessary. when a set of timber fai1s under the Pressure of swelling ground, there is no immediate fall of timber and broken rock to fill the drift, as is customary in heavy, caving ground. Instead, ground swelling from sides, top and bottom gradually closes the opening, over a period of weeks or months, and no especial hazard to workmen is present while they have room to walk through the narrowing drift. Most

Jan 1, 1946

By G. R. Fitterer

By means of the C-Sic thermocouple1, liquid metal temperatures have been found to vary much more than was previously supposed, and fortunately these variations can be directly associated with some of our former knowledge which combined to form the "art" of liquid-metal manipulation. Commercial Development of This Device Several types of installations are operating in different plants. There are so many variables in steel plants in regard to operation, procedure, arrangement of pouring platforms, ladles, etc., that most of the installations now in service in this country are "tailor-made"; nevertheless, it is felt that satisfactory gains have been made, inasmuch as each installation has indicated some effect of temperature upon the metallurgical operation, and has pointed the way toward technical and financial benefits. In most cases, it has been necessary to accumulate the temperature data until sufficient metallurgical information is available for the drawing of conclusions. When mechanical difficulties have been eliminated, a distinct correlation of these factors has been obtained. The installations now in service are used for the determination of temperatures in the basic open-hearth furnace prior to tapping and in ladles from both acid and basic furnaces prior to pouring. Some of the installations are in shops making the higher priced steels; others are in "tonnage shops." The errors of human element, smoke screens and emissivity corrections connected with the use of the optical pyrometer do not affect the C-SiC thermocouple readings. The accuracy of the C-Sic thermocouple and the temperatures measured are discussed later in this paper. Temperature Variations or Liquid Pig Iron One well-known discussion between the blast-furnace and open-hearth (or Bessemer) departments has occurred intermittently for more

Jan 1, 1936

By G. R. Fitterer

By means of the C-Sic thermocouple1, liquid metal temperatures have been found to vary much more than was previously supposed, and fortunately these variations can be directly associated with some of our former knowledge which combined to form the "art" of liquid-metal manipulation. Commercial Development of This Device Several types of installations are operating in different plants. There are so many variables in steel plants in regard to operation, procedure, arrangement of pouring platforms, ladles, etc., that most of the installations now in service in this country are "tailor-made"; nevertheless, it is felt that satisfactory gains have been made, inasmuch as each installation has indicated some effect of temperature upon the metallurgical operation, and has pointed the way toward technical and financial benefits. In most cases, it has been necessary to accumulate the temperature data until sufficient metallurgical information is available for the drawing of conclusions. When mechanical difficulties have been eliminated, a distinct correlation of these factors has been obtained. The installations now in service are used for the determination of temperatures in the basic open-hearth furnace prior to tapping and in ladles from both acid and basic furnaces prior to pouring. Some of the installations are in shops making the higher priced steels; others are in "tonnage shops." The errors of human element, smoke screens and emissivity corrections connected with the use of the optical pyrometer do not affect the C-SiC thermocouple readings. The accuracy of the C-Sic thermocouple and the temperatures measured are discussed later in this paper. Temperature Variations or Liquid Pig Iron One well-known discussion between the blast-furnace and open-hearth (or Bessemer) departments has occurred intermittently for more

Jan 1, 1936

By A. W. Bethune, L. M. Pidgeon

The equilibrium vapor pressure of zinc has been determined over the systems: ZnS(s) + Fe(s) = FeS(s) + Zn (vapor) and ZnS(s) + 2Cu(s) = Cu2S(s) + Zn (vapor) by reacting the components in an evacuated tube containing a thin copper fiber, and allowing equilibrium to be established with respect to the brass formed and the zinc in the vapor phase. The composition of the brass formed was determined and equilibrium vapor pressure values obtained from existing data. Between 850' and 1000°C, values for the first reaction ranged from 8 to 58 mm Hg; for the second reaction from 1.8 to 22 mm Hg. THE direct reduction of metallic sulphides may be indicated by an equation of the form MS + X = XS + M [1] where X is some suitable reducing agent. In the case where M is a metal of relatively high volatility, the use of vacuum will displace the equilibrium to the right at comparatively low temperatures in the face of the usually unfavorable thermochemistry. For this technique to be feasible, MS, X, and XS, must of course be nonvolatile compared to M. In this regard, zinc becomes an obvious metal both from the point of view of its volatility and the fact that most commercial ore deposits of this metal occur as the sulphide, and its direct reduction would avoid the expensive roasting process necessary prior to present day reduction methods. Two reducing agents are of interest, namely copper and iron, with the former having the added attraction of being relatively easily regenerated by oxidation in the copper converter. The possibility of these reactions has been considered before. Imbert1 patented a process whereby zinc sulphide was reduced by either copper or iron. The process as described took place at atmospheric pressure and, at the high temperatures required, the system was molten, resulting in the formation of a matte with the consequent reduction in the activities of the reactants. Peterson2 did further experimental work on these reactions and, although promising results were obtained on a small scale, attempts to increase the size of the furnace led to excessive "blue powder" formation. The early workers failed to realize the large reduction in temperature afforded by the use of vacuum and its desirable results. More recently, the direct reduction of zinc sulphide by iron has been the subject of a thermody-namic investigation by Kelley,3 and Gross and War-rington' have studied the kinetics of the reaction in the temperature range 900" to 1000°C, their experiments being conducted using vacuum and indicating that the reaction would proceed practically to completion in 1 to 3 hr, depending on the temperature. A qualitative examination of the system ZnS-Cu carried out at this University indicated that 98 pct of the theoretical zinc in the charge could be recovered in 1 hr at 1000°C when operating under reduced pressure. The purpose of this research program was to study the equilibrium of the two reactions. During the investigation, reference to the experimental work of Schenk5 was found but, due to lack of detail in the report, it was felt that it would be desirable to continue the equilibrium measurements. Selection of Method The measurement of vapor pressure of metals presents obvious problems resulting from the high temperatures which must be employed. In the present case, the production of the "reaction pressure" introduces a further difficulty since a chemical reaction must proceed before any metal vapor pressure is produced, resulting in depletion of the re-

Jan 1, 1954

By H. E. Elliott, R. S. Busk, A. T. Peters

ONE of the problems of the fabricator of metals and alloys is the propensity of some composition ranges toward abnormal grain growth during certain stages of fabrication. In this respect magnesium alloys are no exception among alloys. Fortunately, convenient foundry control methods have been developed by which the abnormal grain growth possible in certain magnesium-alloy castings can be suppressed. An unusual characteristic of magnesium alloys, however, is that castings of some composition ranges are subject to local grain growth during heat-treatment without the necessity of intentional mechanical stressing of the part prior to heat-treatment. This effect occurs only under certain critical casting conditions, and only in certain alloys of greater than about 8.5 per cent aluminum content, such as C alloy (Mg, o per cent Al, 2 per cent Zn, 0.2 per cent Mn) and G alloy (Mg, i0 per cent Al, 0.2 per cent Mn). The first observation of this phenomenon in cast magnesium alloys occasioned much surprise, since it is not observed in other metals. Jeffries and Archer' have stated that "the grain size of cast metals, provided they have not been plastically deformed, cannot be changed by heating below the melting point." The study of the conditions leading to abnormal grain growth in cast magnesium alloys, and of the mechanism of this phenomenon, has led to some very interesting observations. Perhaps the most significant of these was the observation that stresses originating from cooling contraction in magnesium-alloy castings are the only stresses necessary, under certain conditions, to cause local recrystallization and subsequent grain growth in the casting during heat-treatment. of abnormal local grain growth was a definite problem in the production foundry on C alloy sand castings. Illustrated (Fig. r) is a picture of a casting scrapped because of this defect. A mottled effect is produced in coarse-grained areas by suitable etching solutions. The properties of metal in the affected area are much impaired by such grain coarsening. Ultimate tensile strengths of half the normal value have been measured in metal of this nature. In this paper are described the techniques that have been developed by The Dow Chemical Co. for studying, and in large measure solving, this production problem. Also discussed are studies of the mechanism by which excessive grain coarsening occurs, and the fundamental conditions that produce this effect. The abnormal grain growth discussed in this paper will be referred to as "germination," since this term has been defined' as any process leading to an abnormally coarse grain size. This paper deals only with abnormal local grain growth that may occur during the solution heat-treatment of certain magnesium-alloy castings, as dis-

Jan 1, 1945

By R. Taggart, R. H. Ericksen, D. H. Polonis

Transmission electron microscopy techniques hare been used to study the spontaneous marfensite phase that forms during the thinning of Ti-Cr alloys. The structure of this phase has been found to differ. from the hcp martensite and has been identified as a clisforted fcc lattice. The spordaneous marlensile in this system is interpreted as a metastable isomorph of the equilibriunz TiCr, phase. WHEN thin-foil specimens for transmission electron microscopy were prepared from metastable alloys of the Ti-Cr system, a spontaneous transformation occurred' when the foils contained the untrans-formed 0 phase or two-phase mixtures of the 0 and w phases. The purpose of this paper is to examine the relationship that exists between the crystal structure of the spontaneous product and that of the matrix. The differences between the martensite transformation that occurs in the bulk material and the spontaneous reaction that occurs during the preparation of thin foils are compared with the observations that have been reported for similar phenomena in a commercial titanium alloy.' A spontaneous reaction that exhibits characteristics similar to a martensite transformation has been reported to occur in thin foils prepared from the retained metastable structures of several alloy systems.1'3"7 ~ull~ observed such a spontaneous reaction in 0 brass and attributed the apparent increase in the martensite transformation temperature to a decrease in the non-chemical free energy associated with bulk strain energy. He also showed that the spontaneous product did not have a specific habit plane, but that its orientation relationships to the parent matrix were dependen on the thickness of the transforming region. It has also been pointed out by Breedis6 that in thin films the absence of the constraints imposed by a bulk matrix can cause different requirements for the martensite plate interface and lattice distortion which is reflected bv a dependence of the transformation mechanism on the specimen geometry. In the case of the spontaneous reaction reported for Au-Zn alloys7 a definite habit plane was determined and shown to correspond with the habit plane calculated on the basis of the Bowles and Mackenzie crystallographic theory of the martensite transformation.'- lo EXPERIMENTAL PROCEDURE A series of titanium alloys containing 5.5, 5.9, 6.4: 7.6, 8.0, 11.3, and 18.7 at. pct Cr were prepared from high-purity (iochrome) chromium and iodide-grade titanium by levitation melting. The experimental procedure used for sectioning the alloys and for thin-foil preparation has been reported in an earlier paper.' X-ray diffraction patterns were obtained using a 114-mm Debye-Scherrer camera and Cu-Ka radiation. In order to minimize fluorescent radiation from the specimen, a strip of aluminum foil 0.002 in. thick was placed in contact with the X-ray film. After a specimen was removed from the camera: an additional X-ray experiment was performed, to insure that no spurious lines were obtained due to the presence of the aluminum foil. The interstitial impurity analysis for the alloys used in this study was as follows: oxygen, 100 ppm: hydrogen, 30 ppm: nitrogen, 28 ppm. EXPERIMENTAL RESULTS Electron diffraction patterns were obtained from several individual crystals of the spontaneous marten-

Jan 1, 1970

By James F. Kemp

Discussion of the paper of JAMES F. KEMP, presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 105, September, 1915, pp. 1801 to 1836. WALLACE E. PRATT, Manila, P. I.-I am glad that Professor hemp has referred to the Philippine ores in his paper, inasmuch as I have had the privilege of examining, in a preliminary way, the ores there. I must say, from the resume given us, that the Daiquiri ores seem to be similar in origin and character to the magnetite-hematite ores in Bulacan Province, Philippines. Professor Kemp has also referred to C. M. Weld's description of the magnetite-hematite ores at Hongkong and to the similarity of these ores to the ores at Daiquiri and to those in Bulacan. There is a minor feature of apparent difference in origin in the Hongkong and Bulacan ores. Mr. Weld believes the iron ores at Hongkong to have resulted from the intrusion of the Hongkong granite, a distinctive rock of wide distribution in the Orient, into sedimentaries which are probably of much greater age than those which have been replaced in part by the ores in Bulacan. Associated with some of the ores in Bulacan and elsewhere in the Philippines there is a granite which may be the equivalent of the Hongkong granite; but the Bulacan ores are not related in origin to the intrusion of this granite, which is clearly older than the ores, but to the later intrusion of dikes and small bodies of basic rocks into the granite and into associated tuffs, breccias, and sedimentaries, including limestone. I gather that the intrusives to which the mineralization is related at Daiquiri are also small in volume and later than larger bodies of associated igneous rocks, from which it would appear that the Bulacan ores are even more closely related to the Daiquiri type than are the Hongkong ores. The deposits in Bulacan are inaccessible and are not large, the largest one containing about 1,000,000 tons, according to an estimate based solely on its outcrop dimensions. Ores of similar character, however, occur in Camarines Province in apparently larger quantity and in a situation on the coast adjacent to deep water.

Jan 12, 1915

By Charles R. Austin, Carl H. Samans

In an earlier serics of studies on 18-8 stainless steel at 600º, 700º, and 800ºC.l one pretreatment was used throughout; viz., 15 min. in hydrogen at 950°C., followed by an air quench. Several manufacturers of this alloy since have expressed doubt as to the suitability of the temperature employed, recommending instead the more customary Strauss treatment as promising superior results. In this subsequent investigation on the effects of the temperature of pretreatment several interesting points have arisen, which are described in this paper. Previous work on our equipment had shown a marked difference between alloys of "similar chemical composition" that had been manufactured by different companies. Accordingly, one mill-bar length was selected from which to prepare all specimens. It could then be assumed that any marked differences in creep characteristics would be due to effects resulting from variations in the pretreatment of the alloy. The material was furnished by the Allegheny-Ludlum Steel Co. in the form of 5/16-in. dia. rod, finished by air cooling from a mill anneal at 1950°F. (1066°C.). It was analyzed only for the elements shown: carbon, 0.07 per cent; chromium, 18.73; nickel, 9.46; manganese, 0.40. Three pretreating temperatures were chosen, the specimens being held for 15 min. in hydrogen at either: (1) 1150°C., to conform to the recommended Strauss treatment; (2) 950°C., to compare with the results of previous tests; or (3) 75Q°C., to initiate precipitation of carbides in the material before testing. As the test cross sections were only 1/8-in. dia., air cooling followed the annealing treatment. These treatments permitted two direct comparisons: (1) between the 1150" and 950°C. treatments to indicate the effect of grain size when all carbides were probably in solution at the start of the test; and (2) between the 950" and 750°C. treatments to indicate the effect of carbide "nucleation" for similar grain sizes.

Jan 1, 1940