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By H. Cecil Spicer

THE results described in this article are based on field work conducted during the periods April-May, 1939, and May-July, 1940. The United States Potash Co. is mining potash on Government land under a permit from the Department of the Interior and the geophysical investigation was completed under a cooperative arrangement made between that company and the Conservation Branch of the Geological Survey. The writer, a member of the Section of Chemistry and Physics of the Geologic Branch, was assigned to this investigation. Four definite objectives were in mind for the geophysical work in the studies over the salt deposits. The first was to determine the measure of success that could be attained in this type of work with the resistivity methods that were to be employed. These methods had been introduced into the work of the Conservation Branch by Benjamin E. Jones for the investigation of dam sites, and have been used under his direction by the author for such work. If the method proved to be applicable, an effort was to be made to contour the top of the salt beds and also the other formation boundaries known to be present in this area. Salt-water aquifers were to be studied in an effort to determine their boundaries, and an attempt was to be made to delineate the potash-bearing beds. EARLIER STUDIES Others have made, and reported, resistivity studies over saliferous deposits in different areas. Friedel1 and Messrs. Schlumberger2 reported geophysical work performed in the discovery of the salt domes of Alsace; Carrette and Kelly3described the geology of the same area. Leonardon and Kelly4 published a resistivity curve obtained over the Hettenschlag dome, and a further discussion of this same area was given by the Messrs. Schlumberger5 in a communication. Messrs. Alty6 described studies on salt deposits in which the single-probe method was used. Sinerez7 mentions that electrical methods were tried over salt deposits in Spain. Geoffrey and Charrin8 show a resistivity curve obtained over marl, gypsiferous marl and salt which is similar to that obtained over the New Mexico salt deposits. Kelly9 reported resistivity work performed with the ground comparator of Zuschlag over the salt deposits near Syracuse, N. Y., where the Salina formation is at a depth of 700 to 8oo ft. Some structural studies on the potash basin of Alsace are described by Poldini.10 Another single-probe resistivity study, made over salt deposits in New Mexico, is briefly described by Heiland,11 through the courtesy of Harry Aurand, of the Midwest Refining Co.

Jan 1, 1941

By Charles H. Behre

This paper deals with recent geologic studies in the slate belt of Northampton, Lehigh and Berks counties, Pennsylvania. The work was conducted under the auspices of the Pennsylvania Topographic and Geologic Survey. Three years have now been spent in detailed consideration of the economic geology of this region. In the field, particular attention was paid to the bearing of geology on quarry development and property valuation and the object of this paper is to summarize the results from that viewpoint. Excellent studies of a somewhat similar nature have already been carried out by Bowles,' but with the emphasis upon the details of quarrying and fabricating methods, rather than upon the geologic relations. The Northampton-Lehigh-BeRks District Location The region here discussed lies in east-central Pennsylvania and extends southwestward from Delaware River, on the New Jersey line, to the Schuylkill in north-central Berks County. It is an elongated belt occupying the northern sections of the three counties mentioned and lying along the southern edge of Blue Mountain. Its length is about 50 miles and its average width five or six, though in places it attains a maximum of 10 miles. There are no large cities in the region, but about 10 miles south are Reading, Allentown, Bethlehem and Easton. Railroads serving the slate belt are the Delaware, Lackawanna and Western, and the Pennsylvania along the Delaware River, the Lehigh Valley and Central of New Jersey along the Lehigh, and the Pennsylvania and Philadelphia and Reading on the Schuylkill. In addition, two railroads—the Philadelphia and Reading and the Lehigh and New England—cut obliquely through the slate region to reach the more isolated communities. Transportation facilities are thus excellent. The slate deposits of these three counties are conspicuously unified, both economically and geologically. In general type of marketable

Jan 1, 1928

By D. C. Jones

The term "coal-mine mechanization" is definable in several ways. In its general application it can mean the use of machines instead of manpower in each of the various mining activities necessary for the production of coal—so that under this definition a mine that uses mechanical coal cutters could be classed as a mechanized mine. Common usage, however, insists that a mechanized mine is one in which machines are used for the entire process of mining or extraction and transportation of the coal. For the purpose of this paper, then, the second definition of "coal-mine mechanization" will be used, and practices employed in mines where the greater part of the production is obtained through the use of mechanical loaders and conveyors will form the basis for this discussion. Physical Contact Hazards If we were to group all the hazards that accompany the use of mechanized equipment in a mine, the predominant class would be that which, for want of a better name, might be termed the "physical contact" hazards; that is, all the sources of danger that lead to accidents through physical contact of workmen with machines. A survey of accidents in a group of mechanized mines indicated that this class of hazards may be responsible for more than half the number of accidents in mechanized mining. For example, of 21 mining-machine accidents at one mine, 14 were of the physical contact type; of 14 loading-machine accidents at the same mine, 8 were the result of physical contact. Certain of these hazards are controllable through the use of guards— a guard over the cutting-machine bits when the machine is being trammed from place to place, or a chain or some similar locking device around the cutter chain, so that an accidental blow or push against the bit control will not cause the cutter chain to move. Other hazards, such as the possibility of a loader operator having his foot crushed by a crawler tread, or a brakeman being hit by a loader boom swung too far to one side while a car is being loaded, might be subject to control through the use of guard devices, but the reduction or elimination of all physical contact hazards by such methods does not appear feasible. Every accident of the physical contact type should he investigated to discover whether guards could have prevented it, but often the only way in which to combat these hazards will be through the awakened consciousness of each workman as to the danger that exists if he indulges in unsafe practices. A good approach to control of accidents in any mine is the establishment of a set of safety rules or operating rules. The intent of such rules is to provide guides far the workmen to follow in the operation of equipment. Frequently the workmen have no regard for such rules, and observance is obtained only through compulsion on the part of management. An interesting development in connection with-the formation of safety rules occurred during a training program for employees in the

Jan 1, 1947

By D. C. Jones

The term "coal-mine mechanization" is definable in several ways. In its general application it can mean the use of machines instead of manpower in each of the various mining activities necessary for the production of coal—so that under this definition a mine that uses mechanical coal cutters could be classed as a mechanized mine. Common usage, however, insists that a mechanized mine is one in which machines are used for the entire process of mining or extraction and transportation of the coal. For the purpose of this paper, then, the second definition of "coal-mine mechanization" will be used, and practices employed in mines where the greater part of the production is obtained through the use of mechanical loaders and conveyors will form the basis for this discussion. Physical Contact Hazards If we were to group all the hazards that accompany the use of mechanized equipment in a mine, the predominant class would be that which, for want of a better name, might be termed the "physical contact" hazards; that is, all the sources of danger that lead to accidents through physical contact of workmen with machines. A survey of accidents in a group of mechanized mines indicated that this class of hazards may be responsible for more than half the number of accidents in mechanized mining. For example, of 21 mining-machine accidents at one mine, 14 were of the physical contact type; of 14 loading-machine accidents at the same mine, 8 were the result of physical contact. Certain of these hazards are controllable through the use of guards— a guard over the cutting-machine bits when the machine is being trammed from place to place, or a chain or some similar locking device around the cutter chain, so that an accidental blow or push against the bit control will not cause the cutter chain to move. Other hazards, such as the possibility of a loader operator having his foot crushed by a crawler tread, or a brakeman being hit by a loader boom swung too far to one side while a car is being loaded, might be subject to control through the use of guard devices, but the reduction or elimination of all physical contact hazards by such methods does not appear feasible. Every accident of the physical contact type should he investigated to discover whether guards could have prevented it, but often the only way in which to combat these hazards will be through the awakened consciousness of each workman as to the danger that exists if he indulges in unsafe practices. A good approach to control of accidents in any mine is the establishment of a set of safety rules or operating rules. The intent of such rules is to provide guides far the workmen to follow in the operation of equipment. Frequently the workmen have no regard for such rules, and observance is obtained only through compulsion on the part of management. An interesting development in connection with-the formation of safety rules occurred during a training program for employees in the

Jan 1, 1947

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 E. W. Stewart, G. P. Conard, J. F. Libsch

The effects of several additives upon the reduction characteristics of hydrogen-reduced ferrous formate are described. The various additives inhibit sintering of the reduced iron particles by apparently different mechanisms. The magnetic properties of the low density compacts produced from the resulting ultra-fine iron powders were improved markedly. THE permanent magnetic characteristics of ultra-fine iron powder prepared by various means have been a subject of considerable interest and experimentation in the past few years. When such particles are small enough to show single domain behavior, they possess' 1—permanent saturation magnetization, and 2—high coercive force. In the absence of domain boundaries, the only magnetization changes in a particle occur through spin rotation which is opposed by relatively large anisotropy forces. With decreasing particle size, the coercive force tends to increase to a maximum and then decrease because of the instability in magnetization associated with thermal fluctuations. Kittel' has calculated the critical diameter at which a spherical particle of iron can no longer sustain domain boundaries or walls to be approximately 1.5x10-' cm. Stoner and Wohlfarthr in England and Neel4,6 in France have shown from purely theoretical calculations that the high coercive force expected from single domain particles is dependent upon crystal anisotropy, shape anisotropy, or strain anisotropy contributions. Further work by Weil, Bertaut,' and many others has contributed much to the understanding of fine particle theory. Neel and Meikeljohn" have demonstrated that a decrease in particle size below a critical value of approximately 160A leads to a quite rapid decrease in coercive force because of the prevention of stable magnetization by thermal agitation. Lih1, working with powders prepared by the reduction of formate and oxalate salts of iron, has shown the marked influence of powder purity upon magnetic properties. Maximum coercive force was obtained in powders of approximately 65 pct metallic iron content while the maximum energy product, (BxH) occurred in powders of 85 pct metallic iron content. Careful consideration of the preceding theoretical considerations and experimental results has led to the manufacture of permanent magnets from ultra-fine ferromagnetic powders by powder metallurgy techniques. Such work has been done by Dean and Davis," the Ugine Co. of France, and Kopelman." The aforementioned work of Kopelman and the Ugine Co. was concerned somewhat with the effect of various additives upon the properties of hydrogen-reduced ferrous formate. Virtually no work, however, has been published on the effects of additives on the reduction rates of metal formates, although unpublished work by Ananthanarayanan16 howed promise of improved energy product in ultra-fine iron compacts prepared by the hydrogen reduction of a coprecipitated mixture of magnesium and ferrous formate. After consideration of the preceding information, it was hoped that a better balance between the metallic iron content and particle size of the reduced iron powder could be accomplished by a prevention of the attendant sintering of the partially reduced iron powder during the reduction reaction. It appeared possible that magnesium oxide might interpose a mechanical barrier between adjacent iron particles and prevent their sintering together, while metallic cadmium and metallic tin would interpose a liquid barrier which might accomplish the same purpose. The degree to which these materials were effective in accomplishing the foregoing objective and the experimental details associated with the work are reported in the following sections of this paper. Experimental Procedure Preparation of Formate and Oxide Mixtures: To obtain ferrous formate of reproducible reduction characteristics, a slight modification' was made in the technique of Fraioli and Rhoda." A supersaturated solution of ferrous formate was mixed with an equal volume of 95 pct ethyl alcohol and the formate crystals precipitated by stirring and screened to —325 mesh. These crystals were in the shape of elongated hexagons, approximately 4x10 micron in dimension. Various preparations of such ferrous formate, designated as lot 111, were reduced for 2 hr, yielding ultra-fine iron particles of exceedingly reproducible size, metallic iron content, and magnetic properties. The magnesium and cadmium formates were prepared by the reaction of dilute formic acid with their respective carbonates, while the tin formate was prepared by the reaction of dilute formic acid with stannous hydroxide. To evaluate the effect of metallic formate additives in intimate mixture with the ferrous formate, varying amounts of magnesium, cadmium, and tin formates were coprecipitated with the latter. The designations of these materials and their chemical compositions are given in Table I. Due to the differing solubilities of the various formates in aqueous media,

Jan 1, 1956

By L. C. Chang, T. A. Read

Diffusionless transformation in Au-Cd single crystals containing about 50 atomic pet Cd was investigated by means of X-ray analysis of the orientation relationships, electrical resistivity measurements, and motion picture studies of the movement of boundaries between the new and old phases during transformation. The nucleation of diffusionless transformation by imperfections and the generation of imperfections by diffusionless transformation were discussed. THAT connections exist between plastic deformation and diffusionless phase changes has long been recognized. Thus it is often possible to produce a diffusionless phase change in a temperature range, above that in which the change occurs spontaneously, by cold-working the initial phase. Certain aspects of the dislocation theory of the plastic deformation of crystalline solids also provide for a rather direct connection between the processes involved in plastic deformation and in diffusionless phase changes. Heidenreich and Shockleyl have pointed out that simple edge dislocations in f.c.c. metals are probably unstable, and that the more probable lattice imperfections, called extended edge dislocations, consist of two half dislocations separated by a distance of the order of magnitude of 100A. The region about two atomic planes thick between the half dislocations because of this stacking fault may be described as having the hexagonal close-packed structure. Presumably the stacking faults observed by Barrett" fter cold-working f.c.c. Cu-Si alloys resulted from the passage of such half dislocations through the lattice of the initial phase. It is now becoming clear that the development of a detailed theory of the atomic movements involved in diffusionless phase changes will require a consideration of the role played by lattice imperfections, just as such considerations are necessary to the understanding of plastic deformation mechanisms. This point of view has been recently set forth, for example, by Cohen, Machlin, and Paranjpe3 who pointed out the role which might be played by screw dislocations in nucleating diffusionless phase changes. The present paper reports on some aspects of the diffusionless phase change in single crystals of the beta phase alloy Au-Cd which serve to emphasize further the importance of lattice imperfections in diffusionless phase changes. The diffusionless phase change of Au-Cd possesses several remarkable features. One of these is that the interface between the high-temperature beta phase and the low-temperature orthorhombic phase typically moves with a low velocity, in contrast to the behavior observed in the transformation of austenite to martensite. Motion pictures of this slow interface motion have been prepared in the course of the work reported here. Another important feature of the Au-Cd transformation is the small amount of undercooling observed. The reverse transformation occurs on reheating to a temperature only 20" higher than the transformation temperature observed on cooling, and under some circumstances the hysteresis observed is substantially less than this. This narrow temperature range between transformation on heating and cooling is presumably in part a consequence of the fact that the transformation requires a lattice shear of only about 3". Finally, the orthorhombic product phase possesses unusual mechanical properties, as was first pointed out by olander' and Benedicks." After completion of the transformation on cooling the specimen can be severely deformed, yet on the release of load it springs back to its original shape in a rubber-like manner. Explanation of this phenomenon will require an understanding of the lattice imperfections in the orthorhombic structure and, correspondingly, of those in the initial body-centered cubic structure. Single crystals of Au-Cd alloy containing 47.5 and 49.0 atomic pct Cd were prepared from fine gold (99.95 pct purity) and chemically pure cadmium (99.99 pct purity) by melting the alloy in an evacuated and sealed fused quartz tubing and growing into single-crystal form by the Bridgman method. The Au-Cd alloy containing 47.5 atomic pct Cd undergoes a diffusionless transformation from an ordered body-centered cubic structure to an orthorhombic structure when it is cooled to about 60°C, while the reverse transformation takes place when the alloy is heated to about 80°C, according to electrical resistivity studies. The structures of these two phases have been studied by Blander,4 reinvestigated by Bystrom and Almin.e he lines of Debye photo-gram of powdered samples of Au-Cd alloy containing 47.5 atomic pct Cd prepared in this laboratory were identified and agreed fairly well with those of

Jan 1, 1952

By R. P. Aikman, F. G. Miller, J. M. Podgursky

In response to the growing demand for low-sulfur coking coal for iron-making, the coal industry is continually striving to perfect methods for cleaning coal to acceptable ash and sulfur levels while maintaining maximum product yield. By present standards the industry has adequate processes for cleaning coarse coal, (i.e., +28 mesh) at almost any desired specific gravity. However, in the case of fine coal (i.e., -28 mesh) neither of the two existing processes-froth flotation and hydrocycloning-in its present state of development yields products that are comparable in ash and/or sulfur content to products normally obtained from coarse coal processes. The work outlined in this article is part of a larger study directed toward maximum exploitation of froth flotation for fine coal processing. The concepts and data presented are now serving as a basis for designing fine-coal circuits in which improved efficiency is obtained by optimum use of froth flotation with other fine-coal processing methods.

Jan 7, 1967

By J. L. Moriarty, Irving Johnson, H. M. Feder

The crystallization of ternary alloys has been studied as a coprecipitation phenomenon by measuring the substitutional carrying of trace metals with CeCd11 precipitating from liquid cadmium. The Doerner-Hoskins logarithmic distribution law has been found to apply in all cases; the coprecipitation coefficients obtained were: 1.48 (La), 1.06 (Th), 0.63 (Pr), 0.24 (Gd), 0.17 (Sm), 0.13 (U), 0.10 (Er), 0.09 (Sr). Li, Na, K, Ba, Y, Sc, and Zr were not measurably carried. It has been observed that coprecipitation was most extensive for those tracers which form with cadmium an intermetallic compmdnd isostructural with CeCd11 or closely related thereto. For these tracers an inverse relation between Solubility in cadmium and coprecipitation coefficient was noted. THE partition of impurities between the liquid and solid phases of a metal or a congruently melting intermetallic compound has been extensively studied by the methods of zone melting.' However, when the composition of a liquid alloy and of the solid phase crystallizing from it differ grossly, partition of an impurity cannot be investigated in this manner. Partition of the impurity under equilibrium conditions may be studied by investigation of the appropriate phase diagram and partition under nonequi-librium conditions may be studied by observation of coring in the solidified alloys.2 The nonequilibrium case is of special interest in metallurgical practice because many complex alloys are cooled too rapidly to permit the uniform diffusion of impurities throughout the crystallizing phase(s). With this in mind, the present study was undertaken to obtain quantitative data on the phenomenon of coprecipitation via substitutional solid solution in certain metallic systems. It will be noticed that rather than adopting metallurgical ter- minology we have chosen to refer to the partition of impurities during alloy crystallization as coprecipitation.3 In the terminology of coprecipitation the impurity is referred to as the tracer and the precipitating phase as the carrier. From aqueous solution, coprecipitation may occur as a result of adsorption on the surface of the carrier, by occlusion of the liquid within the crystals, or by solid solution of the tracer in the carrier. By slow cooling of liquid metallic solutions it is relatively easy to form large, regular crystals of the carrier; the effects of adsorption and occlusion may be minimized and the influence of substitutional solid-solution formation may be made to predominate. Previous studies of the crystallization of some intermetallic compounds4 and of copper, silver, and gold5 have shown that the coprecipitation or partition behavior of trace metals is entirely analogous to that observed in aqueous systems when ionic substitution occurs, e.g., coprecipitation of Ra++ with BaSo4. The precipitation of CeCd11 from liquid cadmium was chosen for study. This choice was influenced by the following consideration. If the relative atomic sizes of the tracer atom and the atom for which it substitutes determine the tendency to coprecipi-tate, then a lattice having a substitutional site of well-defined size would be desirable. In CeCd116 (structure type cubic BaHg117) the cerium atom is completely surrounded by a cage of twelve nearly equidistant cadmium atoms. Thus, atoms much larger or much smaller than cerium should be poorly accommodated in this cage. The choice of a lanthanide central atom allowed the testing of the size hypothesis with a number of lanthanide tracers which differed in size but not in valence or electro-negativity. EXPERIMENTAL The general technique of this investigation was to prepare a slightly undersaturated solution of carrier in liquid cadmium to which a tracer was added. The concentration of tracer was always so low that saturation over the entire temperature range investigated was never exceeded. The solution was cooled in a stepwise fashion. After each step a por-

Jan 1, 1964

By A. E. Deruyttere, J. Van der Planken, M. Laurent, Van den Bergen

FahRENHORST and schmid1 observed that zinc single crystals work hardened less rapidly when strained in liquid air (- 185°C)than in a bath at -82°C, whereas at higher temperatures the rate of work hardening decreased with increasing temperature, as would be expected. Cadmium and magnesium showed no such decrease at -185°C. At that time the observed anomaly for zinc at liquid air temperature probably seemed insignificant. However it later was confirmed2 by experiments in liquid nitrogen (-196°C) and in the mixture solid carbon dioxide-acetone (-77"C) and therefore appeared to be real. seeger3 then suggested that the anomaly might be due to the different wetting of the zinc crystals by the cooling media. Recently a new confirmation was obtained,4 however the cooling media again were different: the rate of strain hardening was found to be lower in liquid nitrogen and liquid oxygen than in pentane cooled to various temperatures down to -126°C. Ekperiments will now be reported in which the medium surrounding the specimen at the different temperatures was the same, namely gaseous air. The single crystals were made from "Overcor 99.99" zinc. They were grown in a vertical traveling furnace on seeds of nearly the same orientations. The diameter of the crystals was 5 mm and the length between shoulders 140 mm. The brass shoulders were stuck to the crystals by means of araldite. A thin steel wire was fixed to each shoulder and served to fasten the specimen to a Houns-field tensile testing machine. The crystals with the shoulders and part of the wires were surrounded by two concentric cylindrical containers. The coolant. either liquid air or ground solid carbon dioxide, was poured into the outer container only. During cooling the containers rested on a support which was removed when the straining was started. In order to check the temperature which the crystals would attain inside the inner container, a hollow bar of zinc in which a thermocouple was fitted was first mounted in the apparatus as a substitute for a crystal. It appeared that a constant temperature, respectively - 183° and -72°C, was attained inside the bar, if a soaking time of the order of 1 hr was allowed and if the outer container was constantly kept filled. Accordingly, this procedure was adopted for every tensile test. To take account of the large scatter, fourteen tensile tests were performed with liquid air and seven with solid carbon dioxide. The orientation of the crystals and the results are presented in the table, in which the symbols have the following meaning: 1 : temperature x : initial angle between basal plane and specimen axis : initial angle between slip direction and specimen axis a : shear strain at fracture 0: average rate of strain hardening = —-——- 100 t0 and Te representing respectively the critical shear stress and the shear stress at fracture. Despite the scatter of the a- and 8— values which is of the same order of magnitude as in the work reported by Seeger and Trzuble,4 it is evident that the strain hardening rate is significantly lower at -183°C thanat-72°C. The table also contains the average values calculated from Seeger and Trauble's results at the corresponding temperatures: z.e., four results at -183oC and two at-70°, -71°C. These authors calculated 9 in a slightly different way, but this is unimportant. The agreement between the a-values shows that both sets of experiments are comparable despite the differences in experimental techniques. The rates of strain hardening also agree and it may therefore be concluded that the anomaly is not

Jan 1, 1962

By G. Sandoz, D. A. Meyn

The fracture surfaces of specimens of titanium a1loys which exhibited susceptibility to subcritical crack growth in a wide variety of environments, including aqueous solutions, alcohols, hydrocarbon gases, carbm tetrachloride, and dry air, were examined. The dominant and characteristic fracture mode was cleavage. which became mixed with an increasing porportion of ductile fracture modes (dimples. and so forth) as the applied KI was increased. The cleavage plane in all the alloys was oriented at 15 deg from (0001) of the a phase. No indices could be assigned to the 15 deg cleavage Plane because of uncertainty as to which zone it belonged to. SLOW crack growth and delayed fracture take place in certain titanium alloys at stress intensity (KI) lower than the critical values for complete fracture (KIc) found in short-time tests for plane strain fracture toughness.' Such crack growth may take place in very dry air on sustained loading if the alloy contains a sufficient amount of hydrogen and if the stress intensity factor is higher than a threshold value designated KIH.2 Similarly, a number of environments such as water, alcohols, and hydrocarbons may cause slow crack growth provided the stress intensity factor exceeds the threshold value KISCC. In this paper it is intended to examine some fracto-graphic and crystallographic details of this subcritical crack propagation process as related to alloy composition, environment, and stress intensity. It has been previously reported that subcritical crack growth takes place in titanium alloys in aqueous environments by cleavage.2"6 The observations to be described here indicate that in the alloys investigated the mode of subcritical crack propagation is more dependent on the stress intensity during cracking than on the environment. The fracture mode is illustrated with photographs of the fracture surfaces at a wide range of magnifications. The crystallographic character of the cleavage mode is also presented and the results discussed. EXPERIMENTAL APPROACH The studies were made on four titanium alloys— Ti-8A1-1Mo-lV, Ti-5A1-2.5Sn, Ti-7Al-1Mo-lV, and Ti-0.350. Of these four alloys the first two were mill annealed and fine grained. The latter two were noncommercial and coarse grained, having been prepared for other experimental purposes. The crystallographic studies required a large-grain size. Consequently the fine-grained alloys were an- nealed in a vacuum at 1950°F and furnace cooled to produce samples for these studies. This treatment did not alter the microstructure significantly except for grain size. All the aluminum-containing alloys showed primary a with a network of ß-phase particles within the a grains; Figs. 1 and 2 show this microstructure for the specific case of fine-grained Ti-8A1-1Mo-1V. The cracks in the figures will be discussed later. Fractographic studies were made on all the alloys, but the electron fractographs displayed herein are from the Ti-8A1-1Mo-1V alloy in the fine-grained condition. Emphasis was placed on this commercial alloy because considerable information was available on the stress-corrosion cracking characteristics in a variety of environments. Sufficient supplementary studies of the alloy after the anneal to produce large grains were conducted to establish that the stress-corrosion cracking susceptibility and fractographic characteristics were not changed significantly. Thus it could be inferred that the crystallographic data obtained exclusively on large-grained specimens would apply also to fine-grained specimens. Fracture surfaces for study were obtained using precracked cantilever beam specimens loaded as described by Brown. The precracked section of a specimen was immersed in the environment of interest. Values of initial stress intensity factor Kli were chosen slightly higher than KISCC in order to obtain a fairly extensive region of slow crack growth. Fracture surfaces representative of a variety of stress intensity levels could then be examined because in the cantilever beam test KI increases as the crack propagates.

Jan 1, 1970

By R. L. Bell, T. G. Langdon

A technique was developed- for determining the grain strain, and hence the grain boundary sliding contribution, occurring during the high- temperature creep of a magnesium alloy, from the distortion of a grid photographically printed on the specimen surface. The results were compared with those obtained from measurements of grain shape, both at the surface and interrwlly, and it was concluded that the grain shape technique may substantially underestimate the grain strain and overestimate the sliding contribution due to the tendency for migration to spheroidize the grains. ALTHOUGH a considerable volume of work has been published on the role of grain boundary sliding in high-temperature creep, many of the estimates of Egb (the contribution of grain boundary sliding to the total strain) have been in error due to the use of incorrect formulas or inadequate averaging procedures.' One of the most easy and convenient measurements from which to compute Egb is that of v, the step normal to the surface where a grain boundary is incident. Unfortunately, this parameter is also the one associated with the treatest number of pitfalls. Values of v have been used to calculate Egb from the equation: egb =knrVr [1] where k is a geometrical averaging factor, n is the number of grains per unit length before deformation, v is the average value of v, and the subscript ,r denotes the procedure of averaging along a number of randomly directed lines. If the dependence of sliding on stress were assumed, it would be possible, in principle, to calculate k from the known distribution of angles between boundaries and the surface. This in itself is difficult because the distribution depends on the history of the surface,' but the problem is even further complicated by the fact that v depends on other factors such as the unbalanced pressure from subsurface grains.3 However, the great simplicity of the measurement procedure for v makes it highly desirable that this problem of k determination should be overcome. In the present experiments, this was achieved by the use of an indirect empirical method in which the grain strain, eg, at the surface was determined by the use of a photographically printed grid. The assumption here is that the total strain, et, is simply the sum of that due to grain boundary sliding, egb, and that due to slip or other processes within the grains, eg. SO that: Et = Eg + Egb [2] Thus k is given by: In practice, it is customary to indicate the importance of sliding by expressing it as a percentage of the total creep strain; this quantity is termed y (= 100Egb/Et). The determination of Eg from a printed grid within the grains avoids the difficulties due to boundary migration which should be considered when the grain strain is calculated from measurements of the average grain shape before and after deformation. As first pointed out by Rachinger,4,5 however, this latter technique has the particular advantage that it can also be applied in the interior of a polycrystal. Recently, several workers have produced evidence on a variety of materials6-'' to support the observation, first made by Rachinger on aluminum,4,5 that 7 can be very high, 70 to 100 pct, in the interior, even when the surface value, determined from boundary offsets, is very much lower.10'11 Although there have been criticisms both of the shortcomings of the grain shape technique'' and of the different procedures used to determine y at the surface,' it seemed important to check whether measurements of sliding by grain shape gave values of y which were truly representative of the material. In the present experiments, grain shape measurements were therefore made both at the surface and in the interior for comparison with one another and with the independent measurements of grain strain using the surface grid technique. EXPERIMENTAL TECHNIQUES The material used in this investigation was Magnox AL80, a Mg-0.78 wt pct A1 alloy supplied by Magnesium Elektron Ltd., Manchester. Tensile specimens, about 7 cm in length, were prepared from a 1.27-cm-diam rod, with two parallel longitudinal flat faces each approximately 3 cm in length. The specimens were annealed for 2 hr in an oxygen-free capsule, at temperatures in the range 430° to 540°C, to give varying grain sizes, and, prior to testing, the grain size of each was carefully determined using the linear intercept method. This revealed that the grains were elongated -0.5 to 5 pct in the longitudinal direction. Testing was carried out in Dennison Model T47E machines under constant load at temperatures in the range 150" to 300°C. At temperatures of 200°C and below, tests were conducted in air with the polished flat faces coated with a thin film of silicone oil to prevent oxidation; at higher temperatures, an argon atmosphere was used. To determine v,, each test was interrupted at regular increments of strain and the specimen removed from the machine. At the lower strains, when v, was less than about 1 pm, measurements were taken on a Zeiss Linnik interference microscope;

Jan 1, 1969

By W. Wanjokow, H. O. Hofman

In the metallurgical treatment of most metallic sulphides it is usually necessary to carry on a roasting-operation. In some cases the raw ore will have to be roasted; in others the intermediary product, matte, produced in smelting the ore; again, both ore and matte may have to be subjected to oxidation at elevated temperatures. Most metallic sulphides, when given an oxidizing-roast, pass through the state of sulphate before they are converted into oxides. All metallic sulphates are completely decomposed by heat, with the exception of those of lead and bismuth, but the temperatures at which decompositions take place vary with the metals. Some metallic sulphates are converted directly into oxides, others first form basic salts. Alkali-earth sulphates show a behavior similar to that of metallic sulphates, while alkali sulphates do not part with their sulphur trioxide even at elevated roasting-temperatures. The older data on the decomposition of metallic sulphates by heat are only approximations. Thus Kerl' gives the order in which metallic sulphates are decomposed with increasing temperatures as (Ag2, Fe, Cu, Zn, Ni, Co, Mn, Pb) SO,. More recent statenlents give definite temperatures and modify the formerly accepted order of decomposition. But the temperatures given by various observers do not agree. The reasons for this are to be found mainly in the method and manner of carrying out experiments. Four methods have been used: 1. Heating in an evacuated tube; 2, heating in a tube closed at one end, without air-cur-

Jan 1, 1913

By E. A. Steigerwald

E. A. Steigerwald (Thompson Ramo Wooldridge, Inc.1— he authors' results clearly indicate that cracking can be produced by the hydrogen pressure developed during a charging operation. This type of cracking or blistering has also been observed in polycrystalline materials24"28 when the charging conditions are sufficiently severe and is often referred to as irreversible embrittlement since it cannot be removed by a baking treatment. There are additional data, however, which must be considered before a pressure theory can be generally employed to account for all failures which occur as a result of hydrogen. In many cases, hydrogen embrittlement in a tensile test or in delayed failures under static loads is a reversible phenomena which cannot be simply explained on the basis of preexisting cracks generated by the charging operation. It is this aspect of the problem which has prompted many investigators to seek mechanisms other than hydrogen pressure to explain their results.24'n728 Fig. 15 indicates an example where, under specific experimental circumstances, hydrogen embrittlement can occur at liquid nitrogen temperatures. In this case, which has been previously decribed,'' specimens were charged with varying quantities of hydrogen, immediately quenched, and tested in liquid nitrogen (-320°F). A companion set of identical specimens were charged, aged at 300°F to remove the hydrogen, and also tested at -320°F. When the current density was greater than lo-' amp per sq in., embrittlekent occurred in both sets of specimens, indicating that cracking had occurred during charging and the embrittlement, as in the case of Fe-Si single crystals, was irreversible. At current densities between approximately 103 and lo-' amp per sq in, the embrittlement was present only for those specimens which contained hydrogen during the testing sequence. The embrittlement was therefore reversible with respect to the aging and charging operations. Since extensive hydrogen movement would not be expected at -320°F, it is difficult to reconcile these data with a mechanism which requires pressure and pressure dependent growth of preexisting cracks. There are other features of hydrogen embrittlement such as the reversibility of the incubation time for delayed failure with respect to applied stressg0 and the influence of prestraining31 which are also difficult to explain using a pressure model. Any general mechanism of hydrogen embrittlement will have to consider the reversible aspects of the embrittlement data as well as the irreversible portion which has been clearly presented for the Fe-Si crystals and which is consistent with a pressure model. A. S. Tetelman and W. D. Robertson (authors' reply)—he authors agree with Dr. Steigerwald that a general mechanism of hydrogen embrittlement must be applicable in all cases where embrittlement occurs. Dr. Steigerwald's experiments were performed on an iron alloy which has an extremely complex microstructure, and therefore does not lend itself to the direct and detailed observations that can be made in Fe-Si. The change in the characteristics of cracks as a consequence of annealing at 300°F is not really known in detail but it is probable that stress-relaxation (blunting) occurs, dislocations produced near the crack tips will be pinned by carbon atoms, and hydrogen will be lost to the atmosphere. Any, or all of these effects of annealing will alter the ease with which a crack subsequently propagates under applied stress. A quantitative treatment of the problem must take these effects into account. Since diffusional processes are presumably eliminated at -320°F, the general mechanism proposed by Dr. Steigerwald's colleagues cannot be operative at this temperature. A detailed discussion of the general' inapplicability of this mechanism has been presented elsewhere. However, the data presented by Dr. Steigerwald in his discussion can be explained in terms of a pressure model. Crack propagation under internal pressure P and applied stress occurs when where is the total energy expended in creating new surface area and by plastic work at the crack tip. The total crack length increases with increasing current density, since we have shown that it systematically increases with hydrogen concentration and Dr. Steigerwald has shown that hydrogen concentration increases with current density. For large L (high current density) Eq. [I] can be satisfied even if P = 0 and the embrittlement process does not require the presence of hydrogen. Specimens charged at a lower current density will con-

Jan 1, 1963

By L. W. Kempf

DURING the recent development of aluminum alloys for free-cutting screw-machine rod, it became desirable to know something of the solubility of lead and bismuth in liquid aluminum and in some aluminum alloys. The literature is not particularly helpful in supplying this information. These portions, therefore, of the constitutional relationships of aluminum-ismuth and aluminum-lead alloys were investigated by thermal analysis and by chemical analysis of samples taken from aluminum-rich melts in equilibrium with precipitated lead or bismuth. The solubility of lead and bismuth in some liquid aluminum-copper alloys was also investi-gated. Some consideration was also given to the solubility of these elements in solid aluminum. Among the earliest investigators of the aluminum-lead and aluminum-bismuth systems was Wright,1 who reported that melts of aluminum and lead formed two layers indicating limited liquid solubility. Under his conditions, the aluminum-rich layer was reported to contain 1.91 per cent Pb and the lead-rich layer, 0.07 per cent Al. Subsequently, Pecheau2 found that in aluminum-rich alloy melts with more than 10 per cent Pb three layers were distinguishable. He reported that the middle layer contained from 3 to 10 per cent Pb. He also found that the melting point of aluminum appeared to be lowered slightly by the addition of lead. Gwyer3 investigated these alloys and found evidence of a slight lowering of the freezing point of aluminum by the addition of either lead or bismuth. He found no evidence of solid solubility in either case and made no attempt to determine the liquidus curves. Hansen and Blumen-thal4 reported that the addition of lead distinctly lowered the solidifica-tion point of aluminum. They also found that bismuth lowered the melting point of aluminum. Guillet5 reported almost complete mutual immiscibility for the aluminum-bismuth alloys in the liquid state. Bohner6 examined the effect of various concentrations of lead and bis-muth on the electrical conductivity of aluminum. He found decreases in conductivity on annealing at 500° C. as compared with the conductivity of the same alloys on annealing at 300° C.

Jan 1, 1938

By C. Fairhurst, A. M. Starfield

As a practicing mining engineer, I face many rock mechanics' problems daily and would like to mention one or two examples to illustrate the current gap between laboratory investigations and actual field problems. I would like to endorse Dr. Obert's suggestion that more field measurements and observations should be undertaken. There is an ever-increasing body of data beginning with Hast's results in Sweden,l then measurements at Elliot Lake, Canada, and so on, including our own measurements at White Pine, which clearly indicate that the horizontal stresses underground are often at least as large as the vertical stresses. Visual obsenation of the deformation of roof and pillars (including failure due to horizontal compression) also demonstrates that the horizontal stresses are often most important. Yet almost every laboratory investigation begins with the assumption that the only stresses acting are vertical. Roof spans in layered formations. for example, are calculated on the assumption that the rock behaves as a gravity loaded beam. This is all too often unrealistic. Roof bolts are also often considered to be simply means of suspending the gravity loaded beams. As Dr. Reed has mentioned they are probably, in fact, acting to restrain a beam which is attempting to buckle due to lateral pressure. The fact that moisture can reduce the strengths of some rocks as much as 50 percent has been known for many years. In the mine me are almost always faced with wet rock, yet no one has investigated ways in which this wakening effect can be overcome. as, for example, by waterproofing the rock. C. Fairhurst, University of Minnesota I would like to mention that we have found,2 from stress-relief determinations, that appreciable (over 1000 lb per sq in.) horizontal pressures occur also at the surface in granites quarried in central Minnesota. Whilst I agree that more field measurements are desirable, it is important to point out that most university research is undertaken by graduate students who must attend classes daily. Their research is therefore restricted to the laboratory. A.M. Starfield, University of Minnesota No one denies the importance of obtaining: data from field measurements. It is equally important, however, that field measurements be guided by theory. Much time and money can be wasted by indiscriminate measurement. An example of the value of theory in interpreting measurements is given in Dr. Obert's comments on the time dependent strain observed in a salt mine. He anticipated that the stress at the wall of the opening would change with time because salt is viscoelastic rather than elastic. It can be shown from theory that if an excavation in a viscoelastic medium is unsupported, then the stress at the wall does

Jan 1, 1967

By N. N. Breyer, W. R. Warke, S. Dinda

A model for the low-temperature peak, LTP, in fcc metals is presented. In high stacking fault energy metals, e.g., aluminum and nickel, it is proposed that a reversible dislocation glide and climb process might give rise to the observed high relaxation strengths and activation energies equivalent to volume self-diffusion values. In low stacking fault energy metals such as copper, gold, and silver, dislocation climb is energetically unfavorable at T < 0.5 Tm and the relaxation process is therefore mainly one of reversible glide. This model is used to explain the effect of a change in grain size and impurities on the LTP. THE low-temperature grain boundary damping peak, LTP, in spectroscopically pure aluminum,&apos; copper,17&apos; gold,2 nickel,3 and silver4 has recently been the subject of a detailed investigation by our laboratory. The main results are summarized in Table I. An empirical relationship was found between the peak relaxation strength, AE, and the width of the dissociated dislocation, do,* given by: do = µa2/24p? (Ref. 5) [I] where p is the shear modulus, y is the stacking fault energy,6-8 and a is the lattice parameter, Table 11. 4E is plotted against do in Fig. 1. Two regions are apparent: region (a)! which contains all but one of the metals, where AE decreases linearly with increasing do, i.e,, AE 1/do; and region (b), where ?E is approximately independent of do. A similar trend is observed when the ratio Qp/QL is plotted as a function of do, Fig. 2. (Qp and Ql are the activation energies for the peak and for lattice diffusion, respectively). In the past, when Qp and QL were found to be comparable, the relaxation peak was explained in terms of grain boundary sliding.10 The equivalence of Q, and Qb. the activation energy for grain boundary diffusion, prompted the suggestion that it was a consequence of reversible grain boundary migration on an atomic scale." A new model for the LTP, which is based on the experimental relationships in Figs. 1 and 2, is presented. In region (a) it is suggested that stress relaxation occurs through the reversible glide and climb of grain boundary dislocations; in region (b) only reversible glide can take place. The resultant effect on the grain boundary might be sliding or "a bowing out", but, since the total distance moved will be 50A, the atomic movements are considered of primary im- portance. It must be emphasized that this is only a qualitative model, but at the moment it appears the most likely way to explain the widely varying, but re-

Jan 1, 1969

By Harold Markus, Gerhard Derge

THE first paper1 of this series described a technique of careful surface preparation by means of which reproducible results may be obtained from potential measurements of the behavior of tin in carbonate solutions with a pH range from 8.4 to 11.2. It then went on to establish the behavior of pure tin electrodes under these conditions and showed that the metal remains active at all times, though the steady potential attained after several hours decreases from I.I2[t] volts at a pH of 12.6 to 0.6 volts at a pH of 8.4. This behavior may serve as a norm with which all other data can be compared. In the second paper,2 small amounts of other anions were added to the carbonate solutions and the conclusion was reached that the common impurities encountered in alkaline materials packaged in tin do not increase corrosion. In fact, in some cases these anions may actually promote the formation of protective films. The present paper rounds out this survey by presenting data on the influence of cations added to the carbonate solutions, as well as the effect of alloy additions to the tin. In many cases the potential data are supplemented with weight-loss measurements. Information is also presented on the effects of some additional anions, the influence of gases above the electrolyte, the behavior of high-purity tin, and the effect of atmospheric oxidation on the corrosion resistance of the above-named alloys. Analysis of the entire body of data discloses some general rules applicable to corrosion in carbonate solutions. The experimental methods used are the same as those previously described. EXPERIMENTAL DATA Cations.-The carbonates of the cations K+, Li+, NH4+, which are soluble, were studied in the same way as the anions, by adding 0.01 mol of the metal carbonate to one liter of 0.2 M sodium carbonate solution, pH 11.2, or to 0.1 M sodium bicarbonate, pH 8.4. The other metallic carbonates are only slightly soluble, of the order of 0 7-3 mols per liter or less, and the sodium carbonate solutions were saturated by adding excess reagent several days before the experiment, shaking frequently, and filtering just before use. The chemicals were c.p. grade in each case except the indium salt. This salt was prepared by solution of the metal in hydrochloric acid and precipitation by addition of Na2CO3. These cations may be divided into two classes, according to their effect on the potential behavior of the tin: (I) normal, (2) passive. To offer a basis of comparison, curves I of Figs. I and 2 are given to illustrate the behavior of tin in carbonate solutions saturated with CaCO3. These curves are the

Jan 1, 1941

By Pedro Bolsaitis, Paul M. Sullivan

The activities of zinc in liquid Zn-A1 alloys in the temperature range of 1000&apos; to 1160°K were determined by means of the isopiestic technique. The results are in reasonable agreement with the previous values determined by the radioactive tracer dew point method. Slightly negative excess entropies of mixing were found. The measured activities suggest that the a function for these alloys is not a constant, as has frequently been assumed, but is better represented by two straight line segments of different slopes. THE thermodynamic data of Al-Z alloys have been the subject of investigation by many authors. However, in the recent compilation of such data by Hult-gren et al.,5 the conclusion is reached that none of the previous measurements are reliable or consistent with each other. Since then two new sets of measurements have been reported,2, 8 both laying claim to good accuracies, yet showing very significant disagreement in the measured activity coefficients of zinc in Zn-A1 alloys and in the magnitude and sign of the excess entropies of mixing. Information on the thermodynamics of the system is of particular interest for interpreting results of the Bureau of Mines research on refining of zinc by distillation of die cast scrap. The present study was undertaken as an independent check on the recent values obtained from dew point measurements 8 and electromotive force measurements.&apos; The isopiestic method, first introduced by Herasy-menko,&apos; was chosen because it is one of the few thermodynamic techniques which, in principle at least, is carried out under perfect equilibrium conditions. The disadvantage of the method is that data are obtained at various random compositions and temperatures, which makes the interpretation somewhat cumbersome. The random errors arising from temperature gradients and fluctuations appear to be comparable to those of other techniques, as evidenced by the magnitude of the estimated uncertainties in the calculated integral thermodynamic quantities. An advantage of the method is that each run provides a relatively large amount of data; thus, it is less time consuming than those methods where samples of each composition must be measured individually. EXPERIMENTAL PROCEDURE The activities of zinc in liquid Zn-A1 alloys were measured by the isopiestic method which uses the principle of the tendency toward equilibrium of a series of samples at various temperatures under an imposed vapor pressure of the more volatile component (i.e., zinc, in this case). The basic apparatus is shown in Fig. 1. The small graphite crucibles that contained the metal samples were 15 mm ID and 13 mm deep with approximately 3 mm wall thickness. Each crucible was notched at the top and bottom to allow easy passage of vapor from one to another. At the beginning of an experiment each crucible was weighed on an analytical balance. Zinc and aluminum of spectrographic purity (99.999 pct) were then weighed into the crucibles. The amounts of each metal added were such that initial compositions varied above and below equilibrium values. One crucible contained only pure zinc. After weighing, the crucibles were stacked with the pure zinc on the bottom (corresponding to the lowest temperature in the furnace) and richest aluminum alloys at the top. The entire stack of crucibles was then placed in the silica glass container "E" which was then sealed under vacuum. Sixteen to twenty calibrated Chromel-Alumel thermocouples were attached by wire along the length of the silica tube, one or more adjacent to each sample.

Jan 1, 1970

By J. W. Pugh

PREFERRED orientations in cold-rolled body-centered-cubic metals appear to have remarkable similarity. The as-cold-rolled textures in iron,1,2 silicon-iron,3 mild steel,4 molybdenum, vanadium,&apos; chromium,&apos; tantalum,&apos; tungsten,&apos; and a-zirconium-niobium alloys10 have been determined. These textures have, in some cases, been represented by congrUOUS pole figures and have all been described in one or both of two ways. They have frequently been reported as predominantly (100) <011> orientation

Jan 1, 1959