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By A. G. Metcalfe, A. Siede

The hardening of annealed copper during fatigue testing appears to be independent of the applied stress and to occur largely within the first 4000 cycles. Copper hardened by fatigue is more resistant to annealing than copper hardened by static means, and softens by a multistage process. Creep studies at 300°C show that copper hardened by fatigue also has greater resistance to creep than statically hardened copper. Some theoretical explanations are discussed. RECENT interest in the behavior of metals subjected to fatigue stems from observations of phenomena which could not be explained by current theories of the structure of metals. In 1953 Bullen et al.l showed that the hardening caused by fatigue at low stresses did not cause severe bending of the lattice as did hardening by static methods. This was later confirmed by Wood, 'and Broom and Ham.3 Clarebrough et al4 showed that as the stress level used in fatigue hardening was increased, bending of the lattice was introduced, eventually approaching that of metals deformed by conventional cold-working methods. The type of hardening introduced by fatigue has other interesting characteristics. Kemsley5 showed that copper fractured by fatigue at low stresses resisted annealing as compared to copper hardened an equal amount by static means. The work of Clarebrough etal, shows that the manner of energy release during annealing differs for fatigue-hardened and statically hardened metal in both magnitude and temperature range of release. In addition to hardening of the lattice, fatigue has been shown to cause softening in materials previously hardened by static methods,5 and also in age-hardened alloys.7 The superposition of a small fatigue stress on the static loading of high-temperature alloys has been shown to increase their resistance to creep.' The present work was an attempt to determine the relationship between fatigue hardening, resistance to annealing, and the creep properties of pure copper. EXPERIMENTAL PROGRAM The program described here was designed to answer three questions: 1) Can stress-cycle combinations well below the failure values give significant increases in hardness? 2) Does hardening, under different stress-cycle combinations, give increase resistance to annealing? And if so— 3) Does superior resistance to annealing confer superior creep properties over statically hardened material? Three-quarter hard OFHC copper was annealed in vacuo at 550°C for 1 hr to produce a strain-free material having a fine grain size and uniform hardness. (The standard deviation of the mean hardness of the annealed samples was less than + 1.9 Dpn). Annealing was performed after machining the fatigue specimens so as to avoid work-hardened surfaces. Jigs were used to avoid distortion. The fatigue properties of the annealed copper were determined using an accurately aligned Baldwin-Sonntag SF1-U machine operating at 1800 cycles per min. This limited the minimum number of cycles which could be examined to about 4000 stress reversals. Since failure resulted in specimen damage, hardness increase with number of cycles was measured by testing specimens fatigued to different fractions of the failure values. The results are shown in Fig. 1, and are superimposed on the S-N curve of the copper in Fig. 2. The resistance to annealing of fatigue-hardened material was compared to that of material hardened by uniaxial tensile straining. Specimens hardened to equal values by both methods were progressively annealed for 1 hr at temperature in vacuo. After each annealing treatment the hardness was measured using a Leitz Durimet hardness tester with a 500-g load. At least five tests were made for each hardness determination. The standard deviation for individual specimens varied from 0.26 to 1.48 hardness points. The results are shown in Figs. 3 to 5. The discontinuous nature of the annealing process has been brought out by drawing idealized curves through the data points. This can be justified by the consistency of the results as well as by general agreement with results of Kemsley.5 The creep resistance of fatigue-hardened and

Jan 1, 1960

Forty-three years ago a record for low cost was made at the Spanish mine, in Nevada county, California. In 22 days of September, 1887, there was mined 2796 tons of ore at a cost of 37.5 cents per ton, of which 32.4 cents was for labor and 5.1 cents for supplies. The mill treated this ore for 23 cents per ton, of which 12.3 cents was for labor and 10.7 cents for supplies. Thus the total operating cost was 60.5 cents per ton. The yield was $1.16 in gold per ton, leaving a profit of 56 cents per ton, or 48 per cent of the yield. The mine was an open-cut in a schist formation on a hillside and the work was done by Chinese laborers that were paid $1.40 per shift. The ore was soft, and could be ground effectively in four Hunting- ton mills, supplemented by silvered amalgamating plates.* The engineer in charge was F. W. Bradley, a student from the University of California. As has been indicated, the conditions were unusually favorable in respect of softness of ore, accessibility to the mill, metallurgic simplicity, with cheap labor and power, but even at that the results were so remark- able as to attract general attention, which, as might be expected, was magnified, for advertising purposes, by the manufacturers of the Huntington mill, the firm of Parke & Lacy, at San Francisco. The record made at the Spanish mine therefore found its way into many textbooks on mining published at that time. The editor of the 'Mining and Scientific Press'† (at that date, Charles G. Yale) evidently took a warm interest in. the

Jan 1, 1932

By C. W. Hazelett

This paper is a resume of some of the accomplishments in direct rolling of strip from molten metal, and a description of some experimental developments in recent years. In all the early developmental work, we used a pair of rolls with a bath of metal between them, maintained by flanges or plates at the ends of the rolls. These flanges produced an excess cooling of the metal and built up enormous pressures at this point as the metal went through the bight of the rolls. Many means were tried for compensating for this excess cooling, such as thickening the strip at the edges, heating the end dams directly or by flowing more of the molten metal against them, leaving an open crotch below the end dam and above the bight of the roll, where the excessive pressures built up could be relieved by some of the metal squeezing out at this point, and so forth. All of these helped somewhat to solve the problem, so that very large heats of many metals melting up to 200°F., having commercially uniform gauges, could be rolled up to 24 in. in width. The rolls were made by mounting heavy rings on heavy shafts, and pressures up to 75,000 lb. per inch in width were used. Cooling of the rolls was generally done by spraying water on the outside surface of the rolls that came in contact with the molten metal. Roll life was commercial with brass, barely satisfactory with copper, and totally impractical with steels. The greatest difficulty encountered in all this work was caused by lack of uniformity in the product, owing to a folding action in the mill. Those who are familiar with the operation of a rolling mill know that a bar entering a mill moves at a lower speed than the peripheral speed of the roll. However, the metal solidifying from a bath in a direct rolling mill is cast at exactly the peripheral speed of the roll. This results in irregular folding of the metal, some irregular remelting of the previously solidified sections, and it is difficult, if not impossible, in some cases to exert enough pressure to weld these folded sections sufficiently into a sound product. In addition to this melange of solid, semisolid and liquid metal in the bath, we know that pressure near the freezing point of any alloy in which the constituents have different melting points—and I believe all of them have—causes the lower-melling-point constituent to be squeezed back until it becomes cold enough to solidify and go through the mill. This segregates all alloys, the segregation increasing with the pressures and the freezing ranges of the metals. Add to these problems the excessive roll-maintenance costs with high-melting-point metals and then, the greatest difficulty of all, the vanity of homo sapiens where a matter of possibly large importance is being considered, and the problems seemed almost insuperable. It was long ago obvious to me that something much more than the size of a corporation's money and self-assuradce was necessary if this process was to be made commercial. I should like to show you first the performance of the only mill we ever really designed and built, to see what might be done with a well constructed mill. We accomplished something new in history with this prccess, first, by producing at Scovill Manufacturing Co. coils of brass

Jan 1, 1945

By Carle R. Hayward

SulphuR has long been one of the banes of the steel manufacturer and often no effort and expense have been spared in order to reduce it to a small per cent. in the finished product. This condition is due to a general conviction that in many cases where steels have failed in service, sulphur has been the cause. But there has been a growing feeling in recent years that the verdict against sulphur has been unnecessarily severe. In cases of segregation it was present in. augmented amounts along with other impurities, but it had not caused the segregation. High sulphur in pig iron is caused by poor furnace conditions and the sulphur is merely one indication of an iron that has not been properly reduced. No amount of subsequent treatment under oxidizing conditions in the open-hearth furnace can remedy the defects, although the per cent. of sulphur may be considerably reduced. In other words, the causes of bad steel can frequently be traced back to bad pig iron, and sulphur is merely one indication that the pig iron is bad. The writer recently visited a steel plant where a mass of evidence had been accumulated which substantiated this fact, and the superintendent was emphatic in stating that high sulphur was not harmful provided the steel was not otherwise poor due to insufficient reduction in the blast furnace. The presence of a moderate amount of sulphur is desirable from the standpoint of the man who machines the steel. The low-sulphur material drags and the production of a smooth surface is very difficult. A slight increase in sulphur enables the machinist to produce a smooth surface without difficulty. Since, therefore, such large quantities of steel are subjected to machining, it becomes highly important that the sulphur controversy should be settled, and if its presence is proved to be harmless the ban on it should be lifted. Among the recent papers on the effect of sulphur on steel is one by Dr. J. S. Unger, Manager of the Central Research Bureau, Carnegie Steel

Jan 1, 1917

By W. A. Wood, H. L. Wain, R. I. Garrod

The mechanical behavior of recrystallized chromil~m of high purity has been studied, principally in torsion and to a lesser extent in tension, at temperatures between —196oand 350oC. Depending upon the conditions of test, the material may show brittle or ductile behavior or an intermediate or subduc-tile state having some of the characteristics of each. This latter state existed at temperatures between approximately ±50°C and was characterized by a) extensive creep at stresses well below the normal fracture stress, b) nonelastic loading/unloading effects during creep, c) strain softening under cyclic loading, and d) final failure of a brittle type. Suggestions are made on the dislocation processes and interactions which give rise to subductile behavior The ductile-brittle transition in bee metals has been studied mainly by tension and bend tests. These methods, however, favor crack propagation which may follow too closely on initiation for detailed study of the transition itself. For work of this nature, therefore, other modes of deformation less favorable to crack propagation may be preferable. This paper describes a study of the ductile-brittle transition in chromium which is based mainly on torsional testing although a few subsidiary experiments were made in tension. It appears to reveal at the transition an intermediate state that cannot properly be described as either brittle or ductile. Torsional tests on chromium have been made by other workers1 but not, as here, primarily for study of this intermediate state. EXPERIMENTAL The chromium, in the form of swaged rod, was prepared by techniques already described.' The particular material used was one in which the main impurities were 0.03 wt pet 0 and 0.006 wt pet N and one in which transition from ductile to brittle states in torsion conveniently fell at about room temperature. For torsion, test specimens were from 5/16-in.-diam rod to provide test portions 1-1/4 in. long by 7/32 in. diam, a twist of 1 deg thereby corresponding throughout this paper to 0.0015 surface shear. The specimens before test were annealed for 2 hr at 1200°C in vacuo, which left them with a re-crystallized grain size of about 0.01 mm, and then electropolished. They were tested under dead-weight loading in an apparatus in which they could be surrounded by a furnace or cooling chamber, tests in practice being made at various temperatures between -196" and +350°C. For tension tests, cylindrical specimens were prepared in a similar manner and tested at room temperature under dead-weight loading. RESULTS (TORSION) Subductile State. The state described above as intermediate between brittle and ductile may be perhaps best defined by reference to torque/twist curves at various temperatures. These are grouped in Fig. 1. Below about -50°C the material was brittle, in the sense that it exhibited little plastic deformation under stress and fractured by cleavage along planes of maximum resolved tension, which in torsion produces the well-known helical type of fracture. The deformation is typified by the curves for -196" and -150°C in Fig. 1; it shows a slight but progressive deviation from linearity above a certain torque, here about 50 lb-in., until fracture occurs at about 95 lb-in. A feature to which it is desired specially to call attention is that under none of the loads did the specimens show significant creep.

Jan 1, 1964

By W. J., Kroll

MOST people believe that rare metals are always, scarce in nature, expensive to make, and therefore useless despite some miraculous properties which might make them a cure-all. There are' some metals, which are quite frequent in nature, such as zirconium, which are called rare only because our present methods for making them are elaborate, thus forcing the manufacturer to sell them at a high price. There are also truly rare metals, such as gallium, which do not occur frequently in ores, but are easily reducible from their oxides. In these cases the price of the concentration operation is the decisive factor. The distribution of the elements in the earth's crust is no indication as to the availability of a metal; the concentration operation is the critical factor. Concentration is frequently obtained in the course of metallurgical operations for the extraction of other metals, and the rare metal may be enriched in by-products, flue dusts, mother liquors or precipitates from electrolyte purification as are indium, thallium, selenium, and tellurium. A periodic table of the rare elements may serve as a basis for discussion of their properties and to establish a program. (Table 1.)

Jan 1, 1946

By A. J. Opinsky

ThE superior performance of nonsag tungsten wire in lamps has been ascribed to the large-grained micro-structure that can be developed in it. The orientations of these large grains have been studied several times; most published data1-' appear to be similar to those plotted in Fig. 1. These new data were obtained by X-ray back-reflection Laue technique from all of the large grains occurring in thirteen different wires that had been heated at the lowest possible temperature for the formation of large grains. Here the wire axis is plotted in terms of the principal directions of the cube. Rosi decided that the preferred orientation of the large crystals could be described by a single ideal orientation, (531), being parallel to the wire axis.' Rieck2,3 and Mannerkoski' have essentially confirmed this finding. Opinsky, Orehotsky, and Seigle argued that the data suggest that (211) is parallel to the wire axis instead of a single ideal orientation.5 This {211} contains the (531) ideal orientation and would appear to be a more general case. Ahlborn and Wassermann report that their orientation data stretch from ( 110) through (531) to (311) 8 This is part of the locus of (211). All these investigators have determined the orientations of the large grains by back-reflection Laue techniques. They have all obtained essentially similar results. On the other hand, Swalin and Geisler, who obtained their data by neutron diffraction, indicated that the preferred orientation of the large grains in doped wire is (110) .7 These findings cannot presently be reconciled with the pole density data described in the previous paragraph. Rosi1 and Rieck2 have advanced arguments about how their orientations could occur. Nevertheless, the crystallographic link between the (110) (cold-worked) fiber texture and the preferred orientation of the large grains has remained missing. This link can be provided through the concept of coincidence-type boundaries. Such boundaries separate two grains that have a certain number of common lattice sites. Coincidence relationships that result from rotations about low index directions are given by Brandon et a1 .' What is desired is a calculation of those orientations that bear a coincidence relationship with the (110) fibers of the cold-worked matrix. This situation arises in the following fashion. Heating the tungsten wire for a combination of time and temperature falling short of the formation of the nonsag structure yields a structure that is still fibrous in nature and the preferred orientation remains (110). During grain growth, the growing grain is in contact with these fibers. It is hence possible that the entire process may begin by the passage of a coincidence boundary into a (110) fiber. The calculations were carried out analytically and checked graphically. Following Brandon et a1.,8 coincidence relationships from 1 in 5 to 1 in 19 have been considered. The results of the calculations are given in Fig. 2. Of the coincidences examined, some of those occurring upon rotation about ( 110) come closest to the experimental points in Fig. 1. Nineteen of the twenty-three data points in Fig. 1 can be attributed to the ideal orientations A, B, C, and D in Fig. 2. As determined analytically, three crystals lie within 4 deg of point A, four lie within 21/2 deg of point B, eleven lie within 5 deg of point C, and one lies within 1 deg of point D-a total of nineteen. The off-lying points are near the |110| point of the triangle.

Jan 1, 1968

By Arthur S. Dwight

From the latest and best literature on lead-smelting, little can be learned concerning the present state of the art of mechanical feeding in the United States. H. O. Hofman, in his Metallurgy of Lead (5th ed., 1899), briefly describes the main features of the system in use at Pueblo, Colo., and later (p. 235) says " the only successful mechanical feeding, as far as the writer is aware, is that found at the works of the Pueblo Smelting and Refining Co." H. F. Collins, in his Metallurgy of Lead and Silver (London, 1899), covers American practice pretty thoroughly; but as to mechanical charging, he says: "The German plan of taking off the gases by means of a small iron pipe suspended in the center, and the plan of charging by means of cup and cone, as in iron blast-furnaces, have both been tried, but have not found favor, chiefly on account of the difficulty of obtaining free access to the furnace-shaft for barring, etc., with such devices."' . H. W. Hixon, in his Notes on Lead and Copper Smelting (3d ed., New York, 1900), gives a description and drawing of the Hixon feeding device, as originally installed at East Helena. Evidence that this system of feeding has passed its experimental stage, and deserves more serious consideration than it has heretofore received, is furnished by two large plants—the Pueblo and the East Helena—of the American Smelting and Refining Co., where mechanical feeding has been in continuous and successful operation for a considerable period; one new plant now erecting at Salt Lake City, Utah, and one old one belonging to the same company, the El Paso works, now being rebuilt after a disastrous fire, in both of which mechanical feeding is to be a prominent feature ; one new plant of an independent concern at Torreon, Mexico, which will adopt mechanical feeding; and a number of other smaller plants, among

Jan 1, 1902

By A. J. Phillips, C. G. Grant, Wm. B. Price

ADMIRALTY nickel is a new corrosion-resisting and heat-resisting white metal alloy composed of 70 per cent. copper, 29 per cent. nickel and 1 per cent. tin. It has been given the trade name "Adnic." In 1924, Wm. B. Price1 described this alloy and its successful use as a diaphragm metal. The physical properties of Adnic at ordinary and elevated temperatures were given in Mining & Metallury.2 A patent3 was granted on Adnic, April 28, 1925. Work was first started on this alloy during December, 1921. An investigation of the patent situation in this country and abroad, and also a search of the literature, did not reveal any work on the ternary diagram, copper-nickel-tin; and the only wrought copper-nickel-tin alloy found was that known as "Newloy," composed of copper, 64 per cent.; nickel, 35 per cent.; tin, 1 per cent. This was being manufactured and sold by Wm. Gallimore & Sons, Ltd., Sheffield, England, for unplated spoon and fork stock, and first came to our attention in January, 1922. The preliminary work in connection with the development of Adnic was started by casting four binary copper-nickel alloys of the compositions shown in Table 1. Various amounts of tin were added to each of these mixtures, to produce the series of ternary copper-nickel-tin alloys also given in Table 1. A 200-gm. sample of each of these was cast by melting in a clay graphite crucible and allowing the melt to slowly cool with the furnace. A longitudinal section from each of these castings was polished and etched for examination. The castings were not homogeneous solid solutions, but showed the usual cored structure associated with cast alloys. However, from an examination of these sections we roughly determined

Jan 1, 1928

By W. H. Smith

IN the course of an investigation on chromium containing minor amounts of alloying elements, the information herein has been obtained on the crys-tallographic orientations resulting from arc melting, rolling, and annealing. The chromium used in this investigation was electrolytic flake obtained from the Electro Metallurgical Co. This material was heated for 20 hr at 1600°C in hydrogen with a dew point of about — 100°C. The oxygen and nitrogen content of the chromium after this treatment was 0.0003 pct 0 and 0.005 pct N. Five pounds of this chromium were arc melted in a water-cooled copper crucible. After arc melting, the oxygen and nitrogen contents were 0.002 and 0.025 pet, respectively. A section of this ingot is shown in Fig. 1. By means of a back-reflection Laue technique, the crystal habit of the cast ingot was determined. As expected, it was found that the [loo] was approximately the axis of the columnar grains. In this respect, chromium behaves like other body-centered-cubic metals in that a cubic axis is normal to the cold surface of the mold. A slab cut from this ingot was rolled at 600°C as follows: four 30 pct reductions were made with intermediate anneals at 1200°C for 15 min. Rolling was done with the [loo] of the columnar grains in the rolling direction. Following the final anneal, an 80 pct reduction was taken at 600 °C. The final sheet thickness was ten mils. By polishing and etching, the thickness was reduced to four mils and the grain orientation determined by the transmission Laue method using molybdenum radiation with a zirconium filter. Fig. 2 is the (110) pole figure for this material with the ideal (100) [011] and (111) [112] orientations indicated. The orientation is typical of most cold rolled body-centered-cubic metals having the [llO] of the grains approximately in the rolling direction and the (100) planes approximately in the plane of the rolled sheet. There is also evidence of some 10) [1 orientation. The grain orientation of sheet rolled 40 and 80 pct in the same direction as before at 600°C followed by recrystallization at 12000 C for 15 min was determined by a back-reflection Laue technique. A random texture was found in both cases. This 1200°C 15 min anneal was found to give complete recrystallization and some grain growth.

Jan 1, 1956

By S. G. Cupschalk, F. A. Dahlman, J. J. Wert

Studies have been undertaken to determine the indicidual effects of particle size, degree of long-range ovder, antiphase domain size, and root mean square stran on the microhardness and yield strength of ordered alloys. Dnta have been analyzed for Cu3Pt initzally ordered to a value of 0.82 and after deformations of 1 and 6 pct. It was observed that deformation fleatly reduced the degree of long-range order. Furtherrnore, wztkin this range of relatively small deforntntlons, the average particle size changed very little while the antiphase domain size was greatly reduced. Smultaneosly, the mcrohardness changed by a factor of two durzng the deforrtation process. PREVIOUS studies have reported some of the effects of cold work on the broadening of X-ray diffraction peaks. These investigations were performed on powder and wire samples representing both ordered and disordered states; i.e., the specimens were initially studied in a severly cold-worked condition. By comparing the difference in line shape between the annealed and cold-worked peaks, fundamental information was obtained concerning particle size, strain distribution in different crystallographic directions, degree of long-range order, and change in antiphase domain size. Considerable theoretical work has been done concerning the analysis of diffraction data obtained from cold-worked metals. Stokes' expressed the change in diffraction profiles in terms of Fourier coefficients. Much of the work in this area has been summarized by warren2 in an extensive review article concerning the analysis of plastic deformation by X-ray diffraction. Cohen and Bever3 applied these techniques in studying the effects of cold work on alloy systems exhibiting long-range order. They utilized the Fourier coefficients of fundamental peaks in conjunction with those of the superlattice peaks to determine the change in antiphase domain size. Little work of this nature has been reported for ordered systems that have undergone small degrees of plastic deformation. The purpose of this investiga-tion was to determine the effects of small deformations in such a material with respect to particle size, strain distribution in various crystallographic directions, antiphase domain size, degree of long-range order, and hardness. EXPERIMENTAL PROCEDURE CusPt was used for the initial investigation since the order-disorder transformation takes place with- out a change in crystal structure. The transformation is readily detectable via X-ray diffraction techniques due to the large difference in the scattering factors of copper and platinum. Additionally, the alloy is relatively low melting (approximately 1300°C) and is easily deformable in both the ordered and disordered states. 1) Specimen Preparation and Cold Working. A 100-g, 12-in. diam., cylindrical specimen of Cu3Pt was prepared by melting and casting 99.99 pct pure Cu and Pt i.n vacuo. Prior to any mechanical working, the material was homogenized in a vacuum for 60 hr at 100O0C, and surface defects were removed by machining to a depth of approximately 116 of an in. The material was then cold-rolled, with an intermediate anneal, into a strip approximately 12 in. wide by 14 in. thick. Straightening and flattening removed another 0.025 in. from the thickness. After a recrystallization treatment at 750°C for 30 min, the specimen was slow-cooled from 55OoC, at the rate of 6°C per hr, down to 150°C to induce superlattice formation. This treatment yielded an ASTM grain size of 7 and a degree of long-range order equal to 0.83 0.06. After obtaining X-ray and Knoop hardness data, the sample was cold-rolled approximately 0.75 pct in one pass through a hand-operated jewelers' mill. X-ray and hardness data were again obtained and the specimen was reduced an additional 5.41 pct in a single pass through the mill. 2) X-Ray Measurements. The specimen was examined in the ordered condition and after the two degrees of cold working previously mentioned using a General Electric XRD-5 unit equipped with a spectrometer and scintillation counter. Using Mo-Ka radiation with a zirconium filter, six orders of the 100 reflection were obtained. It was anticipated that point counting would be necessary for an accurate determination of the low-intensity peaks and tails: however, it was demonstrated that, by using a scanning speed of 0.2 deg per min and the appropriate time constant, the recorded data were sufficiently accurate. Thus, for ease of experimental procedure, all peaks were recorded on chart paper. Specimen position in the holder was considered to be insignificant after making a series of measurements of the same peak area in different positions with respect to the beam. Since peak overlapping did occur at high values of 20, it was necessary to separate the peaks graphically prior to analyzing the data in order to minimize this source of error. The peak tails were also carefully drawn to obtain the best possible data. Fourier coefficients of the line profiles were calculated on an IBM 7072 computer, and graphical meth-ods2j3 were employed in analyzing the results. For this type of calculation, in which the line profile is represented by intensities taken at set intervals, the intervals selected must be sufficiently small to give an accurate representation of the line profile. It was decided that for 20 = 0.02 deg the line profiles were

Jan 1, 1967

By R. A. Swalin, B. W. Roberts

ONSIDERABLE controversy has centered about the existence of an order-disorder transformation in alloys in the composition vicinity of 75 atomic pct Ni and 25 atomic pct Cr. All the evidence to date for such a transformation is of a rather indirect nature, since direct X-ray confirmation is difficult to obtain as a result of the small difference in X-ray scattering factors between nickel and chromium. As a result, superlattice lines would be very faint if present. Several investigators1-5 have observed anomalies in the electrical resistivity vs temperature curves of alloys in the vicinity of 25 atomic pct Cr. The observed change is characterized by a rather broad resistivity peak at about 540°C. A discontinuous drop in resistivity is normally associated with ordering. However, Taylor and Hin-ton4 have rationalized that the discrepancy could conceivably be caused by changes in the Brillouin zones upon ordering. The same investigators measured the specific heat as a function of temperature and have also observed anomalies in the vicinity of 540°C. Nordheim and Grant5 have proposed, because of the absence of superlattice lines and the absence of a discontinuity in the resistivity vs temperature curve, that long-range order is improbable and that the results could be better explained by short-range ordering. To date, however, the question has not been resolved satisfactorily. Neutron diffraction techniques provide a method for partially resolving the question since nickel and chromium have considerably different atomic scattering factors in the case of neutrons and, therefore, superlattice peaks, if ordering occurs, should be readily discernable. The results of a neutron diffraction investigation* coupled with a dilatometric in- vestigation are reported here. An alloy containing 28.0 atomic pct Cr was prepared from carbonyl nickel and electrolytic chromium in the form of a 1-in. diam x 10-in. ingot. Melting was done in an alumina crucible and casting in a graphite mold. The ingot was homogenized at 1250°C for seven days, after which a 5-in. long piece was cut into shavings in order to obtain a suitable neutron diffraction sample. Hardness samples and samples suitable for dilatometric analysis (% in. diam x 2 in.) were prepared from the remainlng piece. The neutron diffraction sample, along with a hardness sample, was annealed at 501°C for seven days, at which time the temperature was lowered to 479°C and held at this temperature for twenty-four more days. The hardness was observed to increase from 133 to 147 Vhn during the course of the annealing treatment, in qualitative agreement with Nordheim and Grant." Neutron diffraction traces taken at room temperature and at 42 °K are shown in Fig. 1. The insert shows the trace taken at room temperature with short counting times and thus only fair statistical accuracy. No evidence for superstructure reflections of Cu3Au-type ordering is observed. The statistical accuracy of the 4.2°K trace was improved by using longer counting periods. Several weak intensities are observed at small angles, including an aluminum reflection from the cryostat assembly and a very

Jan 1, 1958

By Morris Cohen, William P. Kimball

This paper deals with the calculation of the composition of the infinitesimal trace of alloy that transfers from the liquid to the solid state at each temperature during the equilibrium solidification of a binary solid solution, and which thereby enables the compositions of the coexisting liquid and solid phases to follow along the liquidus and solidus lines respectively during the cooling. A general expression for the composition (6) of the liquid-to-solid transfer at each temperature has been derived: d= Zlxl(xl - P) + Zsxs(P - xs)/Zl(xl - P) + Zs(P - xs) [1] where ZL and Zs are the slopes of the liquidus and solidus lines at the given temperature, Xl and 28 are the compositions of the stable liquid and solid phases at the same temperature, and P is the composition of the alloy under consideration. The 6 equation is valid for the process of equilibrium heating as well as cooling, and may be applied to vapor-to-liquid, vapor-to-solid, liquid-to-liquid, and solid- to-solid transfers if the corresponding equilibrium diagrams are known. The d-versus-temperature curves for two alloys P1 and P2 are shown in Fig. I. In each case, the liquid-to-solid transfer has the same composition as the stable solid phase only at the temperature of the beginning of solidification, and has the same composition as the stable liquid phase only at the temperature of the completion of solidification. At each intermediate temperature, the composition of the liquid-to-solid transfer differs by a finite amount from those of the two coexisting phases. Therefore, during equilibrium cooling, the transfers must merge into the solid phase from the liquid without forming a transition phase; otherwise the condition of equilibrium would be violated. At any given temperature during solidification, the composition of the liquid-to-solid

Jan 1, 1941

By Morris Cohen, William P. Kimball

This paper deals with the calculation of the composition of the infinitesimal trace of alloy that transfers from the liquid to the solid state at each temperature during the equilibrium solidification of a binary solid solution, and which thereby enables the compositions of the coexisting liquid and solid phases to follow along the liquidus and solidus lines respectively during the cooling. A general expressioll for the composition (6) of the liquid-to-solid transfer at each temperature has been derived: , = Zlxl{xl - P) + ZsXsiP - xs) [I] Zl(xl -P)+ Zs{P - xs) where ZL and Zs are the slopes of the liquidus and solidus lines at the given temperature, xl and xs are the compositions of the stable liquid and solid phases at the same temperature, and P is the composition of the alloy under consideration. The d equation is valid for the process of equilibrium heating as well as cooling, and may be applied to vapor-to-liquid, vapor-to-solid, liquid-to-liquid, and solid-to-solid transfers if the corresponding equilibrium diagrams are known. The d-versus-temperature curves for two alloys P1 and P2 are shown in Fig. I. In each case, the liquid-to-solid transfer has the same composition as the stable solid phase only at the temperature of the beginning of solidification, and has the same composition as the stable liquid phase only at the temperature of the completion of solidification. At each intermediate temperature, the composition of the liquid-to-solid transfer differs by a finite amount from those of the two coexisting phases. Therefore, during equilibrium cooling. the transfers must merge into the solid phase from the liquid without forming a transition phase; otherwise the condition of equilibrium would be violated. At any given temperature during solidification, the composition of the liquid-to-solid

Jan 1, 1941

By William P. Kimball, Morris Cohen

This paper deals with the calculation of the composition of the infinitesimal trace of alloy that transfers from the liquid to the solid state at each temperature during the equilibrium solidification of a binary solid solution, and which thereby enables the compositions of the coexisting liquid and solid phases to follow along the liquidus and solidus lines respectively during the cooling. A general expression for the composition (6) of the liquid-to-solid transfer at each temperature has been derived: d= Zlxl(xl - P) + Zsxs(P - xs)/Zl(xl - P) + Zs(P - xs) [1] where ZL and Zs are the slopes of the liquidus and solidus lines at the given temperature, Xl and 28 are the compositions of the stable liquid and solid phases at the same temperature, and P is the composition of the alloy under consideration. The 6 equation is valid for the process of equilibrium heating as well as cooling, and may be applied to vapor-to-liquid, vapor-to-solid, liquid-to-liquid, and solid- to-solid transfers if the corresponding equilibrium diagrams are known. The d-versus-temperature curves for two alloys P1 and P2 are shown in Fig. I. In each case, the liquid-to-solid transfer has the same composition as the stable solid phase only at the temperature of the beginning of solidification, and has the same composition as the stable liquid phase only at the temperature of the completion of solidification. At each intermediate temperature, the composition of the liquid-to-solid transfer differs by a finite amount from those of the two coexisting phases. Therefore, during equilibrium cooling, the transfers must merge into the solid phase from the liquid without forming a transition phase; otherwise the condition of equilibrium would be violated. At any given temperature during solidification, the composition of the liquid-to-solid

Jan 1, 1941

By R. J. Mechin

IN the early part of 1934, the St. Joseph Lead Co. purchased from the Kadco Corporation three dust-removal units, two suitable for raise work, and the other for drifting operations. The equipment was installed at the Balmat mine, in St. Lawrence County, New York. The Kadco dust-control system can be briefly described as one in which hoods, through which the drill steel is drawn, control the dust at the drill hole, the dust is conveyed through rubber hose or pipe to a collector, where it is removed from the air stream, and the air is then available for recircula-tion in the working place. As during the last few years a number of studies had been completed for the purpose of determining whether or not the dust was effectively removed by the Kadco system, and as the dust counts taken in these tests apparently indicate that it was, the St. Joseph Lead Co. was only inter-ested in obtaining data to show the efficiency of drilling, expressed in terms of minutes per foot drilled, when -using Kadco equipment, in comparison with the former method of drilling dry in a raise and drilling wet in a drift. Comparative dust counts were taken at Balmat, however, by the Metropolitan Life Insurance Co. to show the difference in the dust content of the air in which the operators worked when drilling dry, wet, or with the Kadco equipment.

Jan 1, 1935

By H. E. Stamm, H. H. Spain, R. C. Rumble

This paper presents a reservoir analyzer study of the performance of the Woodbine formation in the East Texas basin. The study was made possible by the compilation of available information on the configuration. thickness and the pressure drawdown of the formation. The investigation was made of the pressure variations in the basin incident to production from the several Woodbine reservoirs. In addition, the apparent compressibility of Woodbine water was evaluated so that the potential water yield of the formation could be determined. The distribution of permeability of the Woodbine sand and the interference between producing areas were also investigated. In conjunction with this basic study of the Woodbine sand, an acceptable match of the production-pressure relationship in the East Texas Field was established on the analyzer. INTRODUCTION When production is taken from a reservoir contiguous to an aquifer, the resultant pressure gradient causes a water influx into the reservoir. For some years it has been the practice to predict the performance of water drive reservoirs with mathematical equations that relate the water influx into reservoirs to their pressure behavior. A rigorous solution of these equations is quite complex: hence, the conventional method requires the simplifying assumptions that the formation have constant thickness, permeability and poiosity, and that it have a known and regular shape. It is necessary to use performance records of the reservoir in question to determine the equation constants that make the results of the mathematical calculations duplicate the reservoir history. The values of the constants determined in this manner sometimes differ so greatly from theoretical or measured values that the constants appear unreasonable. The equation constants comprise such factors as the thickness, porosity and permeability of the formation, and the viscosity and compressibility of water. Usually the thickness, porosity and viscosity are known within a reasonable degree of certainty. whereas the formation permeability and the water compressibility are known with considerably less certainty. Hence. permeability and compressibility values are arbitrarily selected that will make the mathematical equations duplicate the reservoir behavior. In many reservoir studies the value of the compressibility of water thus selected has exceeded the reported value by a factor of from severalfold to manyfold. Whether this excessive value results from the inadequacy of the mathematical approach to take into account the shape irregularities and the heterogeneities of the aquifer, or is due to some type of formation compaction and decrease of porosity has not been established. Because of the significance of the potential water yield of formations with reference not only to oil reservoirs but to water resources as well, it is very important that a representative value for the effective water compressibility be determined. One of the best known examples of a field for which it has been possible in the past to predict the future reservoir pressure is the East Texas Field. Until about 1943 it was possible by means of mathematical equations to duplicate past pressure behavior and to predict with a high degree of accuracy the reservoir pressure of the field. Since 1943, however, the calculated pressures have deviated progressively from the observed pressures to such a degree that in recent years, it has

Jan 1, 1951

By H. H. Spain, R. C. Rumble, H. E. Stamm

This paper presents a reservoir analyzer study of the performance of the Woodbine formation in the East Texas basin. The study was made possible by the compilation of available information on the configuration. thickness and the pressure drawdown of the formation. The investigation was made of the pressure variations in the basin incident to production from the several Woodbine reservoirs. In addition, the apparent compressibility of Woodbine water was evaluated so that the potential water yield of the formation could be determined. The distribution of permeability of the Woodbine sand and the interference between producing areas were also investigated. In conjunction with this basic study of the Woodbine sand, an acceptable match of the production-pressure relationship in the East Texas Field was established on the analyzer. INTRODUCTION When production is taken from a reservoir contiguous to an aquifer, the resultant pressure gradient causes a water influx into the reservoir. For some years it has been the practice to predict the performance of water drive reservoirs with mathematical equations that relate the water influx into reservoirs to their pressure behavior. A rigorous solution of these equations is quite complex: hence, the conventional method requires the simplifying assumptions that the formation have constant thickness, permeability and poiosity, and that it have a known and regular shape. It is necessary to use performance records of the reservoir in question to determine the equation constants that make the results of the mathematical calculations duplicate the reservoir history. The values of the constants determined in this manner sometimes differ so greatly from theoretical or measured values that the constants appear unreasonable. The equation constants comprise such factors as the thickness, porosity and permeability of the formation, and the viscosity and compressibility of water. Usually the thickness, porosity and viscosity are known within a reasonable degree of certainty. whereas the formation permeability and the water compressibility are known with considerably less certainty. Hence. permeability and compressibility values are arbitrarily selected that will make the mathematical equations duplicate the reservoir behavior. In many reservoir studies the value of the compressibility of water thus selected has exceeded the reported value by a factor of from severalfold to manyfold. Whether this excessive value results from the inadequacy of the mathematical approach to take into account the shape irregularities and the heterogeneities of the aquifer, or is due to some type of formation compaction and decrease of porosity has not been established. Because of the significance of the potential water yield of formations with reference not only to oil reservoirs but to water resources as well, it is very important that a representative value for the effective water compressibility be determined. One of the best known examples of a field for which it has been possible in the past to predict the future reservoir pressure is the East Texas Field. Until about 1943 it was possible by means of mathematical equations to duplicate past pressure behavior and to predict with a high degree of accuracy the reservoir pressure of the field. Since 1943, however, the calculated pressures have deviated progressively from the observed pressures to such a degree that in recent years, it has

Jan 1, 1951

By S. Saito, P. A. Beck

The crystal structure of MoNi3 was determined by means of X-ray diffraction. This structure is isotype with that of ovgered TiCu3. The lattice parameters are: a. = 5.064A, bo = 4.224A, co = 4.448A, and zf 0.157. If the orthorhombic distortion (slight relative to the corresponding orthohexagonal unit cell) is disregarded, the structure may be described in terms of a close-packed ordered atomic layer, stacked in the sequence: abab. The structztres of ordered TiCu3 and TiAl3 are homotectic. The three types of ordered hexagonal phases, iso-structural with TiNi3, MgCd3, and VCo3, are known to occur in AB3 alloys of transition elements of the first, second, ad third long periods. It was noted1 that phases with the TiNi3 structure occur selectively in alloys of Ti-group elements with Ni-group elements. In AB3 alloys of Ti-group and V-group elements with Co-group elements the AuCu3-type structure predominates.' The vCO3 structure, which was determined very recently,' has hexagonal symmetry, but the actual atomic arrangement here, too, is rather closely related to the ordered cubic structure of AuCu3-type. However, an ordered hexagonal close-packed structure of the MgCd3-type occurs in MOCO33 and WCO3.4 Consequently, the question arises as to whether or not the crystal structure of MoNi3 is also of the MgCd3-type. Grube and winkler5 found that MoNi3 has a hexagonal close-packed structure with a = 2.54A and c/a = 1.65. They pointed out that some additional weak diffraction lines could be observed in the powder pattern, which may have been due to an ordered atomic arrangement in this phase. However, no detailed information was obtained by them and the structure was apparently not further investigated by others. The present work was, therefore, undertaken in an attempt to determine in detail the structure of MoNi3, and to investigate the possibility of ordering. EXPERIMENTAL METHODS Alloys used in the present work were arc-melted in a water-cooled copper crucible under helium atmosphere. Electrolytic nickel and molybdenum, both 99.9 pct pure, were used. Chemical analyses were not made, but the melting loss was not higher than 2 pct for any alloy. Ingots were first homogenized at 1200°C for 48hr, quenched, heavily cold worked, and then annealed at 820" or 860°C for 1 week, followed by quenching in cold water. Powder specimens for X-ray work were prepared by crushing the heat-treated solid specimens. In order to remove strains, the powders were reannealed in evacuated scaled fused silica capsules for 6 hr at the same temperature at which the corresponding solid specimens were annealed. X-ray photographs were taken with an asymmetric focussing camera, using unfiltered CrK or CuK radiation. EXPERIMENTAL RESULTS The X-ray diffraction patterns of alloys containing 20.8, 25, and 26.4 at. pct Mo, homogenized at 1200°C, showed the face-centered-cubic structure of the Ni-base a-solid solution. It was revealed, however, by micrographic examination that the 26.4 at. pct Mo alloy contained in addition very small amounts of a second phase, in accordance with the phase diagram.6 On the other hand, the 20.8 at. pct Mo alloy after annealing at 820°C gave the X-ray diffraction pattern of the ordered face-centered-tetragonal MONi4.7 In this pattern several additional weak diffraction lines were also observed, corresponding to the strongest diffraction lines of MoNi3. The alloys containing 25 and 26.4 at. pct Mo after annealing at 820" or 860°C gave X-ray diffraction patterns, as shown in Tables I and 11, corresponding to MoNi3. Each one of the reflections which could be tentatively indexed on the hexagonal close-packed cell of Grube and Winkler,5 with the exception of the basal plane reflections, was split into a doublet, as seen in Table I. Since microscopically the alloy consisted of a single phase, it seemed probable that the lattice of MoNi3 is actually slightly deformed, as compared with the tentative hexagonal unit cell. In addition to these diffraction lines, several weak lines were also present, as shown in Table 11, which could not be indexed at all on the hexagonal close-packed cell considered. Satisfactory indexing of all diffraction lines observed was found to be possible by using an orthorhombic unit cell with ao = 5.064A, ft = 4.224A, and c = 4.448A. These values, whose accuracy is estimated to approximately ± 0.008A, correspond to 95.14A3 for the volume of the unit cell, and to an X-ray density of 9.50 g per cm3. If no attention were paid to the weak reflections listed in Table II, a reduced -unit cell of half the volume (a = 2.532A, b = 4.448A, and c = 4.224A), closely related to the orthohexagonal cell, might be used. The dimensions of the orthohexagonal cell of the same volume as the reduced cell are: a = 2.562A, b = 4.437 A, and c = 4.183A. It may be seen that in the reduced cell the a axis is slightly shorter, while the b and c axes are slightly longer than those corresponding to the orthohexagonal cell of the same volume. This slight orthorhombic distortion is re-

Jan 1, 1960

Jan 1, 1907