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By W. Rostoker, S. A. Spachner

FOLLOWING the discovery of the w transition phase in certain titanium-chromium alloys by Frost, Parris, Doig, and Schwartz, much interest has centered on the alloys in which this phase is found and its mode of precipitation. The w phase has been found in alloys of Ti-Cr, Ti-Fe, Ti-Mn, Ti-MO,2 and Ti-v.3 The temperature-time-transformation characteristics have, as yet, not been determined for most of these. In this study, such transformation characteristics have been investigated for two heat-treatable titanium alloys known to exhibit transition phase phenomena. The alloys chosen, Ti-8Cr and Ti-13M0, are representative of two classes of binary equilibrium systems. In the

Jan 1, 1959

By R. W. Fountain, J. Chipman

THE solubility of nitrogen in iron and steel has been of considerable interest due to the role of nitrogen in strain-aging and in quench-aging. It is generally considered that quench-aging is the result of precipitation of carbide and nitride particles from supersaturated solid solution, while strain-aging results from the segregation of carbon and nitrogen atoms to dislocations.1-9 The rate of strain-aging is controlled primarily by the amount of carbon and nitrogen in solution and the temperature. In experiments on strain-aging of pure iron with only carbon or nitrogen as impurities, Fast" has shown that even after 40 hr at 50°C carbon did not give any strain-aging while

Jan 1, 1959

By P. Ramachandrarao, T. R. Anantharaman

EVER since the technique of quenching metals and alloys from the melt (splat cooling) was perfected a decade ago, it has been recognized that the grain size of products solidified by this technique may be extremely small.' The further observation that fcc metals quenched from the liquid state contain very few dislocations has led to the inference2 that metals are subjected to negligible or no stresses during the rapid solidification characteristic of the "gun" or "piston-and-anvil" technique. Evidence for the incidence of appreciable densities of stacking faults has, however, been obtained in case of some splat-cooled fcc and hcp alloys,3 although not for pure metals. In the light of these earlier observations it was considered desirable to study X-ray line-broadening effects, if any, in fcc metals rapidly cooled from the melt. In the present work pure silver (>99.99 pct), aluminum (>99.99 pct) and lead (>99.9 pct) were quenched from the liquid state from temperatures about 50°C above the melting point by the "gun technique" and the resulting foils were subjected to X-ray examination in a Philips Diffractometer. The quenched foils (up to -10 u thick) did not generally stick to the substrate surface and could be easily transferred to the Diffractometer without introducing any plastic deformation. The profiles of the first five reflections from the foils were recorded in each case with Cu Ka, radiation at the slowest available scanning speed of 1/8 deg per min. To correct for instrumental broadening, profiles were also recorded from the metals annealed in vacuo at suitable temperatures. The integral breadths of the X-ray reflections were arrived at by a procedure described earlier.' There was a distinct suggestion of preferred orientation in the recorded intensities of reflections from aluminum and lead foils. Such an effect was not observed in case of silver. In addition, the integral breadths of X-ray reflections from splat-cooled aluminum and lead were not significantly different from those recorded for the annealed metals. The analysis was therefore continued only for silver where the X-ray line broadening was appreciable. The pure diffraction broadening, B, was evaluated for each X-ray reflection (hkl) from silver from the observed, B, and instrumental, b, breadths with the aid of each of the three equations due to Scherrer,5 Anantharaman and Christian,6 and Warren and Biscoe,7 respectively: Bs= B-b BAC=B- b2/B Table I gives the values of particle size, 71, the lattice strain, E, arrived at by the use of the following well-known relations and on the assumption that all observed diffraction broadening could be attributed to lattice strain or particle size, respectively: E = 1/4 cos ? n= B cos ? where A is the wavelength of X-radiation and 0 is the Bragg angle. As no significant peak shifts or asymmetry could be detected in the profiles from the foils, the possibility of any significant contribution due to twins or stacking faults was ruled out. The absence of faults is by no means surprising since pure silver is known to develop stacking faults only on severe deformation and the stacking fault densities recorded so far for even silver filings have been extremely low.' The very low values for percentage mean deviation from the mean value for the particle size in Table I strongly suggest that all observed broadening in splat-cooled silver can be attributed only to small particle size. This conclusion receives further support from the lowest mean deviation recorded for data computed from the Scherrer equation based on Cauchy profiles that are considered characteristic of particle size broadening. Further analysis for separation of particle size and lattice strain effects was considered unnecessary in view of the very large mean deviations obtained for strain values and also the earlier results suggesting absence of even detectable strain in metals and alloys quenched from the melt. It is to be stressed in this connection that the particles are actually grains and not cells formed by walls of high dislocation density usually encountered in deformed samples. As such, the absence of strains is not surprising. The present results are probably the first to record X-ray line broadening due only to small particle

Jan 1, 1970

THE increased demand for titanium alloys with improved high-temperature creep strengths has stimulated interest in silicon as an alloying addition to titanium. Silicon is a potent solid-solution strength-ener and, if added in sufficient concentration and properly heat-treated, can also dispersion-strengthen titanium by eutectoid decomposition.' However, better understanding of the nature and distribution of the resulting silicide dispersion in more highly alloyed titanium matrices is necessary for the development of useful titanium alloys which utilize the latter strengthening mechanism. This note describes the chemical and crystallographic characteristics of the silicide phase as it occurs in a typical high-temperature near-a titanium alloy matrix. Several Ti-6A1-3Sn-3Zr a11oys containing various amounts of silicon ranging from 0.1 to 1.0 pct were melted as 10- to 20-lb ingots and processed into 1/2-in.-diam bar stock. The microstructures of specimens annealed at various temperatures were conveniently summarized by the (Ti-6Al-3Sn-3Zr)-Si pseudobinary phase diagram illustrated in Fig. 1. Comparison with the Ti-Si equilibrium diagram indicates the substitutional solutes (Al-Sn-Zr) increase the eutectoid temperature and decrease the a terminal solubility. Annealing at temperatures sufficiently high to dissolve the silicon in a ß solid solution and cooling rapidly enough to preclude coarsening generally produced a uniform dispersion of fine silicide particles, whereas annealing at temperatures near but below the ß transus produced relatively coarse silicide particles. Annealing in the limited a, plus 3 region produced a duplex coarse and fine silicide array. Several a-annealed specimens were examined by X-ray diffraction to determine the crystallographic identity of the precipitate phase. Copper Ka X-ray diffraction patterns of bulk specimens which contained 0.5 and 0.8 pct Si were virtually identical to that of the silicon-free Ti-6Al-3Sn-3Zr base alloy except for a slight shift in some of the high-angle diffraction lines. Apparently the silicide volume fraction was too low to be detected in bulk specimens. X-

Jan 1, 1969

E. P. Pfleider, University of Minnesota I would like to ask Bob Merrill whether he considers that horizontal concave curvature of a slope has any stabilizing effect, such as Jenike 1 suggested several years ago. R. H. Merrill, U. S. Bureau of Mines, Denver Federal Center The stabilizing effect is due to the restraint offered to radial movement by the curvature. We found in laboratory tests that if we constrained the rock with the same stresses as those measured in the pit then it would sustain a maximum stress about two or four times greater than when the same rock type was unconstrained. We are therefore definitely of the opinion that a constrained situation in a slope is favorable towards stability. G. A. Leonards, Purdue University I was interested in Mr. Lane's observations concerning the correspondence between rate of slide movement with rise of reservoir. Perhaps the most interesting feature is that the rate of movement at the time the rock slope failed was less than the rate at an earlier time when it did not fail. This is difficult to explain from current slope stability theory. K. S. Lane, U. S. Army Corps of Engineers I believe that reduced rate of movement is the result of the progressive type of failure, such as described by Patton and Deere. which occurs along the sliding surfaces. It is difficult to analytically define the progressive failure condition for inclusion in slope stability conditions, but its existence should be recognized in design. We should also realize that many apparently stable slopes undoubtedly contain overstressed regions. To design a slope with no overstressed region would be uneconomical and conservative. D. H. Deere I would pose the question-"What is the meaning of a factor of safety of one?" We were involved in the design of a large, irregularly shaped, underground cavity with an unsupported span of several hundreds of feet. Tests on rock specimens indicated a strength of 1300 lb per sq in. The RQD would have been between 90 to 100 percent indicating excellent structural continuity. In-situ stress determinations indicated an approximately hydrostatic state of stress at a level of 1400 lb per sq in. Calculation of stress concentrations at the walls indicated that the stresses there would be about 3000 to 4000 lb per sq in. Admittedly the rock is in a confined condition everywhere except at the very skin of the wall and the rock walls would thus on the average be somewhat stronger. Allowing for the effect of restraint the factor of safety was found to be less than 0.5 over a region several feet into the wall. Construction was started, using rockbolts only to support the walls. Failure around the immediate skin occurred after each

Jan 1, 1967

By G. W. Nabor, M. Mortada

The effects of anisotropic or directional permeability on the areal sweep efficiency and the flow capacity are examined. The paper points out the importance of taking directional permeability into consideration in planning a flood. It analyzes the two-dimensional flow pattern associated with the skewed line drive for a unit mobility ratio. The direct and staggered line drives are treated as special cases of the skewed line drive. Analytical expressions are developed for the areal sweep efficiency at breakthrough and the flow capacity. They are related to the spacing between like wells, the distance between a row of injectors and the nearest row of producers, and the degree of skewness of the line drive. The latter quantity is defined such that it is equal to zero for the direct line drive and equals one-half for the staggered line drive. The areal sweep efficiency and the flow capacity depend also on the orientation of the flood pattern with respect to the principal axis of anisotropy. The paper provides a simple method for determining the areal sweep efficiency and the flow capacity for a formation in which the permeability in the bedding plane is anisotropic. INTRODUCTION Directional or anisotropic permeability is manifested by the ability of the formation to conduct fluids more readily along certain preferred directions. This situation occurs in many producing formationsl-4 and is usually attributed to depositional features in which the sand grains are oriented in a preferred direction. In some cases it results from the formation of a major and a minor fracture system. 4 Directional permeability should be taken into account in many phases of the production and exploration activities. Recognizing its existence in the formation of interest and planning accordingly can lead to increased recovery and substantial savings. For instance, the areal sweep efficiency in a water flood depends to a great extent on the orientation of the flood pattern with respect to the principal axis of permeability. Anisotropic5 permeability is specified by the directions of its three principal axes and the permeability along each axis. The principal axes of permeability are mutually perpendicular. This paper deals with the areal sweep efficiency at breakthrough and the flow capacity for formations with aniscltropic permeability. The flood pattern considered consists of alternate rows of injecting and producing wells. The rows of wells are parallel and form a developed, skewed line drive which is illustrated in Fig. 1. The staggered and direct line drives are treated as special cases of the skewed line drive. PRELLMINARY CONSIDERATIONS The formations considered in this paper are assumed to be of uniform thickness and porosity. The permeability is uniformly anisotropic, with each principal axis of permeability maintaining

By J. Skrove, C. R. Boardman

In situ permeability of the rock outside the Hardhat chimney was determined by pressurization of long holes with air. Experimental data indicated a remarkable difference between fracture permeability of the rock near the chimney and that at a considerable distance. Although permeable fault zones were known to exist in the granite stock, the measurements of background permeability were quite low, on the order of tenths to several millidarcies. The observed difference is about two or three orders of magnitude above this background in the region 125 to 215 ft radially from the shot point, or 80 to 165 ft radially from the vertical axis of the chimney. The presence of a collapsed drift immediately beyond this region precluded measurements which could have defined the maximum extent of the zone of high permeabilily. INTRODUCTION Previous exploration has revealed that contained nu-clear explosions create cavities which generally collapse, resulting in rubble-filled chimneys and annular fractured zones. These geometries have been shown to result in complex flow regimes which should increase the production rate from hydrocarbon reservoirs.' Empirical scaling equations have been developed for estimatina chimney radii and heights for a variet; of rock media.' The exten; of the annular fractured zone has been documented and associated permeability changes have been observed qualitatively for several explosions. This study was begun to establish the nature and magnitude of the permeability of the latter region. It is anticipated that results will be useful in estimating permeability changes and consequent production stimulation which might ensue from a contained explosion in a hydrocarbon reservoir. The post-shot environment of the Hardhat event (a 5-kt contained nuclear explosion in granitic rock) was c'hosen for the experimental measurements. The Hardhat device was detonated at a depth of 939 ft, and subsequent exploration revealed a chimney of broken rock with a radius of 65 to 70 ft and a height above shot point of 281 ft.' BeFore the explosion, the Hardhat medium was highly jointed and fractured (Fig. I). Jt was expected that differential rock motion along these and other weaknesses induced during cavity growth and collapse would significantly alter the permeability of the rock mass. EXPERIMENTAL METHOD Initially, three 2-in. diameter holes (Nos. 10, 12 and 19) were drilled about 25 ft outward through the walls of the 500-ft level drift (elevation 4,253 ft, Fig. 2). One was drilled near the chimney and two holes, one vertical and the other horizontal, were drilled near the shaft. Order-of-magnitude differences in permeability obtained by pressurization measurements indicated further: investigation was warranted. A series of 3-in. diameter holes was then drilled with water as a coolant into the walls and roof of the drift (Fig. 2). An 11-in. long packer was set from 1 to 8 Et inside each hole and air was injected at measured Row rates. Hole pressures were monitored at the collar. Permeability was low enough in the holes near the access shaft that pressure could be maintained long enough to obtain good pressure decay rates. In the vicinity of the chimney, however, permeability was so high that this was not possible and air was injected under steady-state conditions. About one year later, these same holes were retested to

Jan 1, 1967

By P. S. Rudman

Crystal-structure occurrences in binary phase diagrams of fifth- and sixth-period elements, zirconium through palladium and hafniun through platinum, are surveyed with the conclusion that average .group number GN is the dominant correlative. This is interpreted in terms of curves of enthalpy differences between competitiue structures that are continuous func -tions of GN. It is further reasoned that the absolute formation energies may also be continuous functions of GN and if so can be simply obtained from the regatives of the heats of sublimation of the elements. It is shown that from such a heat of formation-GN plot the heats of mixing of alloy systems can be quantitatively predicted. For example, for sixth-period alloys very large exothermic heats of mixing are predicted for systems that span GN = 6 (i.e., Hf-Pt, Ta-Os, ...). Thermodynamic data with which to test these predictions do not appear to be available. If in the latter transition (A subgroup) elements we eliminate from consideration the fourth period where magnetic terms contribute to crystal-structure stability, as shown in Table I, there is a very regular sequence of structures. Using the group number (GN) assignments of Table I, which differ from the usual assignments of 8 to the elements listed as 8 through 10, it is perhaps trivial to say that the phase occurrence is a unique function of GN. However, the interesting aspect of alloys from among these elements is that the alloy structures also appear to correlate with GN. The GN for an alloy is given as GN = SixiGNi, where xi and GNi = atomic fraction and GN of component i, respectively. It is difficult to credit anyone in particular with having discovered this correlation, so many people have implicitly or explicitly employed it in the last 10 years. However, Bloom and Grant' in their correlation of s-phase occurrence with total number of d + s electrons were certainly one of the first to appreciate the correlation and Hume -Rothery2 appears to be responsible for the use of average GN as defined above. Only in the last few years have the phase diagrams of enough alloy systems been determined for this correlation to be surveyed with any degree of completeness. We shall here, in an abbreviated format, summarize the available phase-diagram literature and discuss some consequences of the GN correlation. BINARY DIAGRAM SURVEY In Figs. 1 to 3 the phase occurrences are summarized. In Fig. 4 the occurrence limits for the more common structures are summarized. That the GN of an alloy falls within the occurrence limits of a particular structure is a necessary but not a sufficient condition for the appearance of that structure. The preceding figures certainly illustrate that GN is a dominant correlative for structures of these elements. Many of the diagrams have complications, with ordering and other phase changes occurring in intermediate phases, that cannot be clearly accommodated in such a schematic survey and have hence been left out. Such omissions cannot, however, negate the GN correlations discussed here. Relative atomic size is also an important crystal-structure determinant and since atomic size varies quite regularly with GN for these elements it is possible that the apparent GN correlation is basically a size correlation. In Fig. 5 relative size occurrence limits are given for intermediate phases and extended terminal solutions. The relative volume, ?v/(v) - 2(vA - vB)/(vA + uB), has been taken as the measure

Jan 1, 1968

By A. G. Jordan, W. Jeitschko, Paul A. Beck

The occurrence qf the V phase structure /Zr,Co,Ge, type) in ternary syste7ns (titanium, zivconium, niobium, lanta1urn) -(nickel, cobalt, iron)-(silicon, germanium) was incestigated. Nine V silicides and four V gertrlanides were found and their lattice constants are reporled. The lattice constants of twenty-one preri-ously identified E phases (TiNiSi type) are given. The average atomic volumes of these phases are discussed in relation to similar binary phases. ThE occurrence of a phase Ti4Ni4Si7 was first reported by Westbrook. DiCerbo, and peat' who gave it the name "V phase". They also reported the existence of an E phase TiNiSi. Subsequently a systematic study was undertaken in this laboratory to explore the occurrence of E' and V phases3 in related ternary systems. In the meantime the crystal structure of the E phase TiNiSi 4 and of the V phase Zr4CO4Ge 75,6 was determined. In the present paper the details of the V phase investigation and the lattice constants of the E and V phases are presented. V PHASES Alloy specimens of approximately 10 to 15 g were prepared by arc melting under argon (99.996 pct Ar) atmosphere. The starting materials were all of purity higher than 99.9 pct, with the exception of cobalt. which contained 0.14 pct Fe as the only major impurity. The weight losses were in all cases less than 2 pct, in most cases less than 1 pct. The samples were encapsulated in fused silica tubes with sufficient argon to yield about 1 atm pressure at the annealing temperature. After the homogenization anneal. Table I. the specimens were water-quenched. A representative portion of each specimen was then examined metallographically (etchant: 20 pct HNO,. 10 pct HF. 25 pct glycerine, 45 pct H20). Only minor amounts of second- and third-phase particles were observed in the specimens listed in Table I, with the exception of alloys Zr4Fe4Si7 and Ta,Fe,Si,. which contained an estimated 10 pct by volume of foreign phases. X-ray powder photographs were taken with a Seeman-Bohlin type focusing camera and Fe-KO radiation. Of the thirty possible combinations of elements in the ternary systems (titanium, zirconium. vanadium. niobium. tantalum)-(iron. cobalt, nickel)-(silicon. germanium) thirteen V phases could be identified. In the remaining seventeen ternary systems and also in the systems Cr-Ni-Si and (M0.W)-(Ni.Co)-Si no V phase was found at the composition 4:4:7 after annealing at temperatures between 900" and 1200'C. For the determination of the lattice constants of the V phases Debye-Scherrer photographs were taken using the asymmetric film arrangement and CrKcr radiation (ka1, = 2.28962A). Using the positional parameters, as determined6 for Zr,Co,Ge,. Table 11. intensity calculations were carried out for each of the V phases with the aid of a computer program.: Thus unequivocal indexing of the diffraction patterns was greatly facilitated. The lattice constants. Table I. were then computed by a least-squares fit of the high-angle lines with f (0) = cos2 Q as extrapolation function. Only few. if any. very weak impurity lines were observed, with the exception of the three iron alloys Zr,Fe,Si7. Zr4Fe,Ge7. and Ta,Fe,Si7. The agreement

Jan 1, 1970

By Eugene McAuliffe

The management of The Union Pacific Coal Co., which operates a group of coal mines in Southern Wyoming, believes in the value of applied psychology as a productive factor in the work of getting out coal. Operating almost wholly through the medium of mechanical loading machinery, the company has for some years paid a bonus, equivalent to one-half the labor saving made above a determined average output per shift worked, on a given machine. No penalty is attached where the established output is not obtained, but in 1933 the men on one class of machines earned an average premium of $0.633 per shift on 56.4 per cent of the tonnage loaded. On another class of machine, the men earned an average premium of $0.686 per shift on 28.4 per cent of the tonnage loaded An increase of 36 per cent in tons loaded per man-shift has resulted since the program was instituted. This coal company has also been very successful in reducing mine accidents through prizes awarded in an unusual way. At the close of the year, every man whose particular mine section passes through the year without a lost-time accident is given a ticket entitling him to participate in a safety drawing where an automobile is awarded as first prim.. There are also a number of cash safety prizes which are similarly awarded. Some 1500 persons attend the drawing, which excites much interest and attention. The particular plan employed, the payment of production bonus awards and safety prizes, is foundationed upon collective. rather than individual effort, and, once gotten under way, has proved to be substantlally self-cnforcing.

Jan 1, 1934

By Jean Howard

THERE are two mechanisms by which secondary crystals can develop in bcc alloys, namely 1) impurity inhibition and 2) strip-thickness inhibition. This paper reports some studies of each mechanism; the alloys were Si-Fe, A1-Fe, Cr-Fe, Mo-Fe, and Ge-Fe, as well as iron itself. All the alloys, which were of interest as part of a program of work on soft magnetic materials, were made by a powder-metallurgy process, using carbonyl iron (Grade MCP) as the starting material. Earlier phases of the work have already been published. Work described previously1 shows how the oxygen content of the sintering. atmosphere can be used to produce silica in the material which acts as a grain-growth inhibitor. Since then it has been found more convenient to make use of the oxide in the iron powder to control the silica content of the material. The compacts are sintered in vacuum which allows a direct reaction to take place between the iron oxide and the silicon. Details are given elsewhere.4 By this method, and by suitable adjustment of the rolling schedule, material with cube-on-edge secondary crystals has been produced in thicknesses from 0.1 to 0.001 in. in iron containing from 2-1/2 to 4-1/2 pct Si. It was also found possible to process 6-1/2 pct Si-Fe to 0.001 in. This was achieved by refinement of the sintered-compact grain size by using fine-particle silicon (i.e., <200 mesh). The brittleness of the material necessitated hot rolling to 0.020 in., from which thickness cold rolling was possible. If the conditions of sintering and the cold-rolling schedule were correct (i.e., as given elsewhere4 for 3-1/4 pct Si-Fe) secondary crystals of (110) [001.] orientation could be developed. The size of the secondary" crvstals" could not be

Jan 1, 1965

By P. R. Kalischer

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

Jan 1, 1941

By P. R. Kalischer

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

Jan 1, 1941

By R. A. Bergman, C. J. B. Fincham

THERMODYNAMIC properties of many high-temperature systems containing sulfur, such as slags, metal sulfides, and solutions of sulfur in liquid metals, have been studied by means of equilibration with known gas mixtures.&apos;" This method presupposes a complete and accurate knowledge of the thermodynamic data for all possible components of the gas phase at high temperatures. However, a survey of the data available up to 1952 on the thermodynamics of gaseous sulfur species and compounds, by Richardson and Jeffes,&apos; showed that there was considerable uncertainty in the values of the free energies of formation of S, SO, HS, and CS. In many cases, this uncertainty made it impossible to decide whether or not these species would form a significant proportion of the sulfur present in the gas phase in any given system. After the review by Richardson and Jeffes had been published, St. Pierre and Chipman6 measured, by an indirect method, the free energy of formation of SO. This also enabled a clear choice to be made among the three possible spectroscopic values for the dissociation energy of S2 into atoms10 thereby determining the free energy of formation of S from S2, and fixing the free energy of formation of HS more accurately" The main purpose of the present investigation was to measure the free energy of formation of CS, which was still in considerable doubt. For example, at 1600°C, it could be estimated to be +6 +25 kcal per mole,* most of the uncertainty being in the * Based on the dissociation energles of CS6 and S2,5 the heat of sublimation of graphite, and, the assumption that the entropy of formation of CS is the same as that of CO. value of the dissociation energy." A secondary purpose of the investigation was to determine more accurately the equilibrium sulfur pressures over dilute solutions of sulfur in carbon-saturated liquid iron. General Method Dilute solutions of sulfur in liquid iron, saturated with carbon, were brought to equilibrium at 1600" and 1800°C, with known gas mixtures consisting, initially, of A and CS2. After equilibrium had been reached, the melts were quenched and analyzed for sulfur. In the high temperature region of the furnace, an equilibrium was set up between the various possible sulfur species and compounds in the gas phase; namely, CS2, CS, S2, and S. (It can be calculated that the amounts of S6 and S, are negligible at these temperatures:) Morris and Bueh17 and Kitchener, Bockris, and Libermana had previously studied the corresponding

Jan 1, 1958

By J. Chipman, N. J. Grant, H. L. Bishop

In a recent review1 of the iron-oxide activity of simple open-hearth type slags containing lime, magnesia, silica, and iron oxide, it was established that activity values were lacking in the range of slag composition most interesting to open-hearth operators. That is, laboratory experimental results were not available for simple slag compositions having basicity ratios ranging from about 1.5 to 4.0 and iron-oxide concentrations ranging from about 10 to 30 pct. However, in order to estimate iron-oxide activities for the range of slag compositions of interest to open-hearth operators, activity values were calculated using ionic concepts of slags by following the treatment of Flood and Grjotheim.2 A study of these data indicated that the desired slag compositions were probably not obtained due to the limited solubility of the basic constituents lime and magnesia. Thus, it was decided to make additional heats equilibrating molten carbon-free iron with slags containing MnO, P2O5, and A12O3 in percentages commonly found in open-hearth refining slags, and to examine the liquid slag field over a greater composition range than that of the simple slags studied previously. The ranges of the constituents used in the present study are summarized as follows: Metal Pct 0 0.070-0.201 PctMn 0.005-0.142 Slag Pet CaO 24.45-41.90 Pct MgO 3.23- 9.21 Pct MnO 1.13- 9.62 Pct FeO 20.08-48.7 Pet Fe2o3 2.23-10.14 Pct SiO, 3.51-28.50 Pct P2O5 0.23- 3.65 Pct A12O3 0.43- 3.38 The experimental procedure consisted of equilibrating the slag and metal in an induction furnace provided with a carbon-arc slag heater as described previously by Winkler and chipman.3 The data obtained were used to establish both the iron-oxide activity values and the activity coefficients for FeO and MnO in the open-hearth type slags. RESULTS AND DISCUSSION I) Iron-Oxide Activity of Open-Hearth Type Slags—The iron-oxide activities of various iron-oxide contents of the open-hearth type slags, as calculated from the oxygen content of the metal by the method of Taylor and Chipman, 4 are plotted against the molar ratio of bases to acids in Fig. 1. The data represent slag-metal studies carried out in the temperature range 1530" to 1700°C. For the purpose of this study, the constituents CaO, MgO, and MnO are assumed equal on a molar basis in their effect on the iron-oxide activity; and, PO2,5 is calculated as an equivalent to SiO2 and A12O3 on a molar basis. The total iron content of the slag is calculated to FeO and is represented by the symbol (FeO) The points presented in Fig. 1 represent the results of this investigation for iron-oxide slags containing between 1 and 8 mol pct MnO and less than about 2 mol pct each of A12o3 and PO2,5 The curved lines shown in Fig. 1 represent the results of the summary1 of the iron-oxide activities of simple slags of the system (CaO + MgO) - SiOz - (FeO),. The solid portions of the curved lines represent experimental data, and the broken portions represent iron-oxide activities calculated from ionic concepts of slags. The iron-oxide values of the open-hearth type slags of this study are in good agreement with the values of the simple iron-oxide slag system. Only a slight modification is indicated. The results of this study suggest that the line for 20 mol pct (FeO), should be lowered slightly in the basicity range 1.5 to about 3.

Jan 1, 1959

By Sherman L. Pease

An inexpensive and relatively rapid method that can be used by field crews is described. Fluid movement is determined by releasing a tracer (dye) in the well at a predetermined level and, after an interval of time, sampling the well fluid at another level. The testing equipment consists of a combined crusher and sampler unit that is run into the well on a wire line. The rate of movement can be calculated from time-volume relationships. Description of Method It is often desirable to determine whether there is occurring any transfer of fluid from point to point in a shut-in well, and, if so, to measure the rate of movement. When it is desired to examine a large number of wells for possible "thief" sands, the time and expense will be considerable unless the method used is inexpensive and rapid. After experimentation with several possible solutions to the problem, the Production Department of the Shell Oil Co., Inc., developed the apparatus described herein, which has proved satisfactory. Routine operations with it can be carried out by field production crews with a minimum of technical supervision and with negligible investment in equipment. The method is based upon releasing a suitable tracer in the well fluid at a known level, and recovering a sample of well fluid at another level after a measured interval of time. Repetition of this process with different time intervals between release and sampling gives the necessary data. For purposes of illustration, the setup for measuring migration of fluid in an upward direction is described in the following paragraphs. The arrangement of equipment is shown diagrammatically on Fig. I. The elements of the combination unit are the tailpiece, the crushing device, the spacer and the sampling device. The lengths of the tailpiece and spacer are varied to place the crushing and sampling devices in the desired positions in relation to the sands being tested. The crushing device breaks the glass bottle containing the tracer when the tailpiece strikes the bottom of the well and the tension on the sand line is slackened. Because of the open construction of the crushing device, the tracer is quickly and completely disseminated in the well fluid. The sampling device is a suction bailer, which obtains a sample of the fluid surrounding the perforated nipple just before the unit is picked up off bottom. The sample is retained in the barrel by the ball valve for examination at the surface. Normally, on the first run into a well, the sample is obtained near the releasing point of the tracer, and thereafter samples are taken near the base of the upper sand if migration is indicated by the dilution or absence of the tracer in the initial sample. The length of the time interval between the releasing of the tracer and the sampling of the well fluid is varied for successive runs, attempting first to establish the rate within limits and then to define it more accurately by additional runs if necessary.

Jan 1, 1946

By Sherman L. Pease

An inexpensive and relatively rapid method that can be used by field crews is described. Fluid movement is determined by releasing a tracer (dye) in the well at a predetermined level and, after an interval of time, sampling the well fluid at another level. The testing equipment consists of a combined crusher and sampler unit that is run into the well on a wire line. The rate of movement can be calculated from time-volume relationships. Description of Method It is often desirable to determine whether there is occurring any transfer of fluid from point to point in a shut-in well, and, if so, to measure the rate of movement. When it is desired to examine a large number of wells for possible "thief" sands, the time and expense will be considerable unless the method used is inexpensive and rapid. After experimentation with several possible solutions to the problem, the Production Department of the Shell Oil Co., Inc., developed the apparatus described herein, which has proved satisfactory. Routine operations with it can be carried out by field production crews with a minimum of technical supervision and with negligible investment in equipment. The method is based upon releasing a suitable tracer in the well fluid at a known level, and recovering a sample of well fluid at another level after a measured interval of time. Repetition of this process with different time intervals between release and sampling gives the necessary data. For purposes of illustration, the setup for measuring migration of fluid in an upward direction is described in the following paragraphs. The arrangement of equipment is shown diagrammatically on Fig. I. The elements of the combination unit are the tailpiece, the crushing device, the spacer and the sampling device. The lengths of the tailpiece and spacer are varied to place the crushing and sampling devices in the desired positions in relation to the sands being tested. The crushing device breaks the glass bottle containing the tracer when the tailpiece strikes the bottom of the well and the tension on the sand line is slackened. Because of the open construction of the crushing device, the tracer is quickly and completely disseminated in the well fluid. The sampling device is a suction bailer, which obtains a sample of the fluid surrounding the perforated nipple just before the unit is picked up off bottom. The sample is retained in the barrel by the ball valve for examination at the surface. Normally, on the first run into a well, the sample is obtained near the releasing point of the tracer, and thereafter samples are taken near the base of the upper sand if migration is indicated by the dilution or absence of the tracer in the initial sample. The length of the time interval between the releasing of the tracer and the sampling of the well fluid is varied for successive runs, attempting first to establish the rate within limits and then to define it more accurately by additional runs if necessary.

Jan 1, 1946

By J. L. Bruce, G. W. Nicolson

ThE country rock of the Mavrovouni mine of the Cyprus Mines Corp. is hydro-thern~ally altered, disintegrated pillow lava, with very little tensile strength ("short" ground). In places, especially when wet, it is heavy ground, though not extremely heavy except where movement has been caused by underlying or nearby stoping operations. Damage by caving from roof or sides of galleries is not sudden but progressively faster when the size of the cave increases as a result of the fall of small pieces. CeMent and Concrete Linings During early operations, galleries in the country rock were supported by customary mine-timbering methods. Available timber, howcver, was of poor quality and of relatively high price, and replacements were frequent and expensive. Furthermore, the massive sulphide ore bodies required large volumes of fresh air for ventilation and cooling, and it was therefore desirable to provide smooth-lined galleries with low resistance for the introduction of air to the ore bodies. It was also desirable to eliminate hazards of fire in shafts and underground workings insofar as this would be practical. Cement and concrete were relatively cheap, and plans for using these in support of shafts, underground galleries, raises, and chutes, were developed steadily. Circular shafts with diameters ranging from 10 to 15 ft were adopted for all permanent shafts and airways. In places these were lined with concrete poured behind sectional pressed-steel forms especially constructed for this purpose. In other places, they were lined with precast-concrete blocks. It was found that such precast concrete of good quality could be produced on mass production scale and delivered at the mine from most favorable point of manufacture, at a cost of about 25 cents per cubic foot of concrete. This refers to prewar costs. As the use of concrete blocks in circular lined galleries was developed, it was found that there were very great advantages in the reduction of air resistance as compared with customary timber supports. After best methods had been developed, it was found that breakage and replacements were extraordinarily low, averaging only about 11\2 pct per year during a period of about 15 years. Furthermore, it has been possible to reclaim for re-use a very large percentage of the concrete blocks from abandoned galleries. During the history of the operations precast-concrete blocks have been used for lining shafts, raises, ore chutes, galleries, and shaft stations, ranging from 3 to 16 ft id. The thickness of lining has varied from 5 to 10 in.; with 12 in. thickness in a few cases. Junctions of two galleries at angles ranging from about 30 to 60° are usually made of poured concrete behind sectional forms, or of a combination of poured concretc and precast blocks. In nearly all cases it has been found advisable to make the point of the wedge at the junction, of

Jan 1, 1949

By Margaret G. Scroger, Luke L. Y. Chang, Bert Phillips

Using the sealed-system technique, isothermal sections at 1000°, 1400°, and 1700°C for the system Co-W-O hare been determined. The equilibrium data were obtained by microscopic and X-ray diffraction examination of samples winch had been equilibrated in pellet form fit sealed capsules and subsequcelly quenched. The only ternary phase in the system is CoWO, which mells congruentlly at approximately 1280°C. At 1000°C, this ternary phase exists in equilihrinm with all the allows and oxide compounds in the hounding binary systems. At 1400°C, liquid forms in thin oxygen-rick region near the CoWO4 composition and only one phase assemblage in the system (W + WO2 + H&apos;5CV7) contains no In order for tungsten to be used to its full potential as a refractory metal. it is necessary that coatings be developed which will preclude oxidation of the metal. It is true that coatings now in use do protect tungsten for short periods at temperatures near 1700 °C. but no coating has been developed which protects adequately at or above this temperature where the use of tungsten is most required. This situation exists despite the great effort in recent years to develop such coatings. and it has become evident that success in this area can be achieved only after a more fundamental knowledge of the thermochemical and therrnophysical propertics of tungsten oxidation and tungsten -metal oxidation is obtained. In our 1aboratories. a project liclrriel. At 1700°C, tungsten is the ouly solid phase which is stctble, and a large range of compositions melt to two liquids, one metallic and one oxidie. The sealed-system method of etjuilibra lion prevents the determination of the partial pressure of oxygen and the total gas pressure orer the condensed phases at equilibrium. This data is not available and can be obtained only by some other method. We can generalize on these unknowns and indicate that both partial pressure of oxygen and total pressure of the gas phase must increase as compositions change from the W-Co binary toward the oxygen apex and as temperatures increase. has been initiated which is directed at providing some of this fundamental information through a study of metal-tungsten-oxygen reactions and equilibria and the properties of any intermediate phases which result. This paper is based on a part of this program in which the system Co-W-O was studied between 1000° and 1700°C. I) RELEVANT INFORMATION FROM THE LITERATURE A) The Notable Lack of High-Temperature Work on Metal-Tungsten-Oxygen Systems. It should be pointed out that there has been no published report (of which we are aware) which deals with the study of a metal-metal-oxygen system at 1700°C. Also, there has been no report on a complete metal-luugsten-oxgen system at any temperature. As a matter of fact. before this program started. The

Jan 1, 1965

By Gerhard Derge

A series of studies of the corrosion of tin is under way in the Metals Research Laboratory at the Carnegie Institute of Technology. The complete program includes examination of the corrosion properties of high-purity tin and the changes produced in these properties by the addition of varying amounts of alloying elements. Other studies of this subject have been made recently under the sponsorship of the International Tin Research and Development Council, but these researches have been confined largely to the weakly acid environments commonly encountered in the canning industry.&apos; There is little information available regarding the corrosion of tin under alkaline conditions, but such data would be of value, for a large amount of the metal is used under such conditions. The potential measurements to be described were made because they seemed to offer the most rapid method for obtaining a general view of the conditions to be encountered in such service. These experiments will also serve to establish a technique that will be of value in further studies. It must be emphasized that the results reported are those of controlled laboratory experiments and that the conclusions drawn cannot yet be applied to service conditions; rather, they point to the directions in which more exhaustive experimental work may be done to best advantage. Experimental Procedure The first work was devoted entirely to the problem of obtaining reproducible results from a series of potential measurements. Only the methods finally adopted as standard will be described here, except when the variations from these have furnished results of interest. The cell used is shown schematically in Fig. 1. The electrolyte is contained in the vessel A (an inverted bell jar), whose ground top is fitted to the transite-board lid B. The controlled atmosphere can be admitted

Jan 1, 1938