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By S. S. Arentz

PLANNED health and safety programs have become an essential part of American industry because such programs lead to increased operating efficiency, improved labor relations, better public relations, and to substantial savings in compensation insurance. Those of you who have had the unpleasant duty of informing the wife or widow of one of your men of his serious injury or death while on the job, know that all the benefits of a successful safety program do not show on the balance S. S. ARENTZ, Member AIME, is General Superintendent, Nevada Operations, Combined Metals Reduction Co., Pioche, Nevada. AIME San Francisco Meeting, February 1949. TP 2741 A. Discussion of this paper (2 copies) may be sent to Transactions AIME before March 31, 1950. Manuscript received Jan. 6, 1949. sheet. These programs are of particular importance to the mining ,industry because mining's reputation as an unusually hazardous industry and the commonly isolated location of mining operations tend to focus attention on these problems. Description of Operations: Before proceeding with a discussion of our health and safety programs at Pioche, it may be proper to give a brief description of Pioche and of our operations there. Pioche is one of the early Nevada mining camps. It was founded shortly after the discovery of high grade silver ore in 1863 and mining has continued with more or less regularity to the present day. In an era of lawlessness, Pioche was notorious. The story persists that 75 men died with their boots on before one died a natural death, and old payroll records show that nearly as many gunmen were employed to stand off claim jumpers as there were miners working the mine. That was probably as close to a safety program as the times permitted. Pioche is situated in southeastern Nevada on the main highway between Ely and Las Vegas. The camp is on the flank of "Treasure Hill," near the original silver discovery, at an elevation of about 6000 ft. The present day population of about 2000 is primarily dependent upon the mines of the area, although Pioche also serves as the county seat of Lincoln Couqty and as the center of the surrounding livestock industry. The camp is served by a branch of the Union Pacific Railroad and receives power from the generators at Hoover Dam. The Pioche operations of the Combined Metals Reduction Co. were started in 1923 when the first complex lead-zinc ore was shipped to the company's mill at Bauer, Utah. The modern mill at Pioche was completed in 1941. The operations are medium sized in the nonferrous field, employing an average of 350 men in the mine, mill, and related works. The complex lead-zinc ore is mined from replacement deposits in a comparatively flat, extensively faulted, limestone horizon. Mining methods vary from stull-supported open stopes to filled square-set stopes. The thin bedded limestone and shale overlying the ore is allowed to cave as areas are mined out and caving frequently follows closely upon ore extraction. The relatively heavy ground and the numerous faults add to the problems of safe mining. The mine is well mechanized and the mill and surface plant are modern and well equipped. Labor is organized in a C.I.O. union and labor-management relations have been unusually harmonious. During most of the period since 1923 a competent supervisory staff worked to reduce safety hazards but the primary responsibility for safety rested on the individual workman. Accidents happened and all too frequently they were regarded by all concerned as unavoidable. In October 1939, the late Robert L. Dean became superintendent at Pioche. Most of his previous experience had been in the fields of iron and coal mining and from that experience he brought the concept that no accident is unavoidable. Many of the features of our present health and safety programs were initiated by Mr. Dean during his term as superintendent. Health Program: Our health program centers in Dr. Q. E. Fortier and his new, well-equipped, and well-staffed, modern hospital in Pioche. The program starts with a thorough pre-employment physical examination and is followed by yearly re-examinations at the expense of the company. The Pioche Mutual Benefit Association, to which all Pioche mine operators and employees belong, pays benefits covering hospitalization and surgery expense incurred by employee members and their families. The Association is governed by a board of directors elected by its members. The mine operators of the district donated the original capital and pay the monthly dues of the employee members. The employees pay the dues covering members of their families. Though not strictly a part of the

Jan 1, 1951

By C. H. Samans, G. F. Tisinai, J. K. Stanley

The addition of nitrogen (0.10 to 0.20 pct) to Fe-Cr-Ni alloys of simulated commercial purity results in a real displacement of the u phase boundaries to higher chromium contents. The effect is small for the (Y + s)? boundary, but is pronounced for the (y + a +s)/(y + a) boundary. Although there is an indication of an exceptionally large shift of the n boundaries to higher chromium contents, especially in steels with nitrogen over 0.2 pct, the major portion of this apparent shift results from the fact that carbide and nitride precipitation cause "chromium impoverishment" of the matrices. The effect of combined additions of nitrogen and silicon to the Fe-Cr-Ni phase diagram is demonstrated also. Nitrogen can nullify the effect of about 1 pct Si in shifting the (y + o)/? phase boundary to lower values of chromium at all nickel levels from 8 to 20 pct. NItrogen can nullify this U-forming effect of about 2 pct Si at the 8 pct Ni level, but not at the 20 pct Ni level. The alloys studied were in both the cast and the wrought conditions. There are indications that the u phase forms more slowly in the cast alloys than in the wrought alloys if both are in the completely austenitic state. The presence of 6 ferrite in the cast alloys accelerates the formation of U. Cold working increases the rate of o formation in both cast and wrought alloys. THE major improvement in Fe-Cr-Ni austenitic alloys in recent years has been in the addition or removal of minor alloying elements to facilitate better control of corrosion resistance, sensitization, and heat resistance. One shortcoming of the austenitic Fe-Cr-Ni alloys, which never has been completely circumvented, is their propensity toward u formation. In the AISI-type 310 (25 pct Cr-20 pct Ni) and type 309 (25 pct Cr-12 pct Ni) steels, sufficient amounts of u phase can form, if service or treatment is in a suitable temperature range, to cause severe embrittlement. Also, there is a growing conviction that this phase may be contributory to some unexpected decreases in the corrosion resistance of certain of the 18 pct Cr-8 pct Ni-type steels. The present paper discusses the effect of nitrogen additions on the location of the (r+u)/d and the (y+a+u)/(y+a) phase boundaries in the ternary Fe-Cr-Ni system, for cast and wrought alloys of simulated commercial purity, and in similar alloys containing up to about 2.5 pct Si. The objective is to define compositional limits for alloys which will not be susceptible to u formation when used near 1200°F (650°C). An excellent review of the early studies of the u phase in the Fe-Cr-Ni system has been compiled by Foley.1 Rees, Burns, and Cook2 have determined a high purity phase diagram for the ternary system, whereas Nicholson, Samans, and Shortsleeve3 are- stricted themselves to a portion of the simulated commercial-purity phase diagram. Both groups of investigators show almost an identical position for the commercially significant (y+u)/y phase boundary. Further comparison of the work of the two groups indicates that, below the 8 pct Ni level, the commercial alloys have a decidedly greater propensity toward u formation than the high purity alloys. The two groups of workers agreed that both the AISI-type 310 (25 pct Cr-20 pct Ni) and the type 309 (25 pct Cr-12 pct Ni) steels are well within the (y+~) region and that the 18 pct Cr-8 pct Ni-type alloys straddle the U-forming phase boundaries. Nicholson et al.3 showed, in addition, that these boundaries shift toward lower chromium contents if greater than nominal amounts of silicon or molybdenum are added. The effect of nitrogen on the location of the s phase boundaries in the Fe-Cr-Ni system has not been known with any certainty. In 1942, an approach to this problem was made by Krainer and Leoville-Nowak,' but at that time they apparently were unaware of the slow rate of s formation in strain-free samples and aged their samples for insufficient times, e.g., 100 hr at 650°C (1200°F) and 800°C (1470°F). For this reason, it would be expected that their (y+ u) /y boundary would be shifted toward lower chromium contents (restricted ?-field) when equilibrium conditions were approximated more closely. Procedure for Studying the Alloys The alloys used were prepared in the following way: Heats of 200 lb each were melted in an induction furnace. A 5 lb portion of each heat was poured into a ladle containing an aluminum slug for de-

Jan 1, 1955

By Charles F. Hickey, Eric B. Kula

Thermomechanical treatments applied to the maraging steels include a) cold working in the austenitic condition at 650°F, followed by transformation to martensite and aging, b) cold working in the murtensitic condition and aging, and c) cold working in the aged condition with and without subsequent reaging. The strength increases in these steels are very small compared to the increases observed in conventional carbon and alloy steels. The changes that are observed are compatible with the strengthening mechanisms operative during thermomechanical treatment of conventional steels, however. Differences are caused by the absence of a carbide precipitate and the low work-hardening rate in both the solution-treated and the aged conditions. ThE 18 pct Ni maraging steels represent a class of steels which are finding great interest for high-strength applications.1~2 They are essentially carbon-free, and contain 7 to 9 pct Co, 3 to 5 pct Mo, and 0.2 to 0.8 pct Ti. Although austenitic at elevated temperatures, they can be air-cooled to room temperature to form a martensite, which because of the absence of carbon is relatively soft. On subsequent reheating age hardening occurs and strength levels of 250 to 300 ksi yield strength can be attained. These steels appear to be particularly suitable for studying the response to various thermome-chanical treatments for additional reasons other than the obvious one of attempting to improve their already attractive properties. Thermomechanical treatments can be defined as treatments whereby plastic deformation, generally below the recrystal-lization temperature, is introduced into the heat-treatment cycle of a steel in order to improve the properties. With an absence of intermediate transformation products on air cooling the maraging steels have good hardenability and hence can readily be cold-worked in the austenitic condition prior to transformation to martensite. Further, they can be worked in the martensitic condition prior to aging, and even can be deformed in the fully aged condition. Finally, it is of interest to compare their re- sponse to that of the more conventional alloy and carbon steels, where the role of carbides is important in the strength increase by thermomechani-cal treatments. The thermomechanical treatment of conventional steels has been the subject of a recent review.' I) MATERIALS AND PROCEDURE The steel used in this investigation was a commercially produced vacuum-melt heat, which had been rolled to 0.090 in. and mill-annealed. The composition of the alloy was as follows: 0.02 C, 0.08 Mn, 0.10 Si, 0.009 P, 0.009 S, 18.96 Ni, 7.34 Co, 5.04 Mo, 0.29 Ti, 0.05 Al, 0.004 B, 0.01 Zr, and 0.05 Ca. Unless otherwise stated the heat treatments used were the standai-d solution treatment at 1500°F for 1 hr, air cool, followed by a 900°F, 3 hr age. In this condition, the material exhibited 232 ksi yield strength and 239 ksi tensile strength. Mechanical properties were determined by Vicker's hardness measurement (20 kg) and by tensile tests on standard 1/2-in.-wide, 2-in.-gage-length sheet tensile specimens. Notch tensile tests were run using the 1-in.-wide NASA type, edge-notched specimen.4 Fracture-toughness determinations were made on 3-in.-wide, center-notched, fatigue-cracked specimens, following the recommendations of the ASTM Committee on Fracture-Toughness Testing.4 An electric-potential technique was used for measuring the crack size at the onset of rapid crack propagation5 which is necessary for calculations of Kc, the critical stress-intensity factor under plane-stress conditions. The critical stress-intensity factor under plane-strain conditions KI, was also calculated, using the stress at which the first observable crack growth occurred. 11) RESULTS A) Cold-Worked in the Austenitic Condition. The reported M, temperature for the 18 pct Ni maraging steel is about 310°F.1 Therefore, a temperature of 650°F was selected as suitable for rolling in the austenitic condition. Specimens were solution-treated at 1500°F for 1 hr, air-cooled to 650°F, and rolled varying percentages from 0 to 60 pct, at 20 pct reduction per pass. Tensile and hardness properties after aging at 900°F for 3 hr are shown in Fig. 1. The tensile strength increases from 253 to 271 ksi and the yield strength from 247 to 265 ksi as a result of a reduc-

Jan 1, 1964

By R. F. Shurtz

R. Duval (Mining Engineer, Ancien eleve de PEcole Polytechnique, Paris, France) I do not agree with the Eq. 3, reading: m =1/100- [(0.214x30.4) + (0.7B6 x0.00)] =6.5pct CaO If 0.214 and0.786 were proportions by weight, the equation would represent the well known mixtures law of the conventional arithmetics and 6. 5 pct CaO would be the correct average content. But it is not the case as the author states: "In samples consisting of single grains of mineral, those grains must, as already mentioned, be either of dolomite or magnesite. Since 78.6 pct of the deposit consists of magnesite and 21.4 pct of dolomite (excluding for present purpose the presence of other minerals), for any single grains picked at random the probability will be 0.214 that is it dolomite and0.786 that is it magnesite. In 1000 such samples the expected numbers of dolomite and mapesite grains will be 214 and 786 respectively." 0.214 and 0.786 would be proportions by weigbt under the necessary condition that all grains of dole mite and magnesite should have an identical weight. Obviously it is not the case, as the specific gravities are not the same for mapesite and dolomite and the volumes of the grains are different. Furthermore, because of these differences the conditions for a random sampling are not fulfilled and we are not authorized to state that the probabilities are, respectively, 0.214 and 0.786. The author however makes a simple application of Eq. 1: M = 1/n— ? fi x i . n Should we deduce that this relation is wrohg? Not at all, but when applying Eq. 1 you must not overlook what it actually. means. Eq. 1 gives a definition of the arithmetic mean of a total of n observed values Xi and nothing else. But the average conteht of a deposit has not the same significance. It is the ratio between the weight of concerned mineral in the deposit and the total weight of the deposit. As from 1000 particles the 214 of dolomite and the 786 of magnesite have not the same weight, the two definitions do not concur, and when applying Eq. 1 the result is an arithmetic mean of figures which has no connection with what is named average contentof a deposit. The situation is similar to the calculation of an average velocity. If a car travels a first mile over at 30 miles per hr and a second mile over at 60 miles per hr, when applying formula 1 you find as average velocity for the 2 miles: 30+60 ------- - 45 miles per hour. Many people calculate in this way and they do not realize that a mistake is involved. In fact the definition of he average velocity for the 2 miles is the quotient of the distance of 2 miles by the time (in hours) necessary for 2 miles travel, i.e.: 2 ---------- = 40 miles per hr. 1 + 1 30 60 In other words, the average volocity wanted is not the arithmetic but the harmonic average of the two velocities. The above mentioned bias in the calculation of the average contents of deposits is frequent, even in the assessments made by experienced engineers and is independant of what is named the sampling error. In order to supress the bias and to be able to use Eq. 1, you must apply a correction. An example on the subject can be found in an article by Duval et al. in the January 1955 issue of the ''Annales des Mines" (French), page 19. R. F. Schurtz (Author's Reply) Mr. Duval's position is quite correct. The proportions shown for dolomite and magnesite., respectively, of 0.214 and 0.786 are, in fact, proportions by weight uncorrected for specific gravity. In our day to day operation of producing magnesite from these mines at a very substantial rate, we do not normally make corrections for the difference between the specific gravity of dolomite and that of magnesite. If these corrections are made in Eq. 3 as shown in my article, then the numbers of grains turn out to be in proportions of 0.226 dolomite and 0.774 mapesite instead of the values actually shown in the equation. For the purposes of our work, and in view of the inherently low accuracy of the data, this correction was not deemed worthwhile making.

Jan 1, 1961

By G. P. Tiwari

Recrystallization and grain growth in thoria dispersed nickel and nichrome were recently studied by Webster as a function of temperature and deformation. The unexpected part of these results was that specimens which had received heavier deformation developed greater resistance to recrystallization. Retardation of recrystallization was accompanied by the formation of voids around thoria dispersion. To explain these results, Webster suggested that the formation of void around the particles increased the effective size of thoria particles. This resulted in greater impediment to the grain-boundary migration and as a consequence the recrystallization of the matrix is retarded. In the present note an alternative and more probable explanation for the effect of voids on recrystallization is presented. The exact mechanism of void formation in thoria dispersed nickel or nichrome is not known. However, it is reasonably certain that it must be preceded by the stress concentration in the matrix around thoria dispersion during the deformation.'' The resulting stress concentration must be sufficient enough to supply the surface energy for the new surfaces created. Further, the decrease in the strain energy of the matrix surrounding the potential void nucleus must be larger than the surface energy of the newly created surface. The release of strain energy due to formation of crack results in a strain free cylinder of the material around the voids.13 If the void formation is not localized, at few points only (as is the case here), this process may lead to considerable amount of release of strain energy of the matrix. The pattern of recrystallization behavior of single phase homogeneous matrix as well as the matrix having a second phase dispersion is same except for the fact recovery and recrystallization are more clearly delineated.14 In general, the recrystallization temperature is lowered (i.e., recrystallization is easier) with increase in the amount of cold work. This is due to the increase in stored energy in the matrix with increasing amount of deformation. If somehow there is a relaxation of strain energy in the matrix, the recrystallization should become difficult because of the decrease in the amount of stored energy available for recrystallization. Since the formation of voids leads to a decrease in the strain energy of matrix, the recrystallization of the matrix would be inhibited due to the formation of voids during deformation prior to recrystallization. It has been observed by earlier workers15'16 that the presence of preexisting voids in a matrix retards the recrystallization. The essential issue here is how do the voids act to produce this effect. If the voids influence recrystallization only by blocking the grain boundary migration, then the effect should be maximum when they are present almost exclusively along grain boundary. These conditions are obtained during high temperature deformation. However, the voids produced due to creep along grain boundary are not able to prevent recrystallization17 suggesting that they are not effective in blocking grain boundary movement. Recently it was shown by Davies and Williams that the voids can act as sinks for vacancies." As a result the processes dependent on vacancy diffusion like recovery, recrystallization, dislocation climb, and so forth, will be hindered. This fact may be responsible for inhibition of recrystallization during subsequent deformation and annealing cycles. It is to be noted here that there is a large difference between the density of voids in creep experiments and the other experiments where retarding effect of voids on recrystallization is seen. The voids in former may number up to l04 to l05 per sq cm whereas in latter cases the voids density is typically around 1010 to 1013 per sq cm. It appears that the decrease in supply of vacancies in creep is insufficient to adversely affect the recrystallization due to low void population. The author is grateful to P. Das Gupta and S. P. Ray for helpful discussions. Author's Reply D. Webster Tiwari appears to have misunderstood the nature of grain boundary-particle interactions. Tiwari (quoting Cahn) states that second phase particles become more effective as they become smaller, therefore as the voids in TDNiC make the thoria particles effectively bigger their ability to resist grain boundary movement is impaired. This particle size argument was originally proposed in the form of an equation by Zener 20 years agol9 and is not necessarily valid as is discussed below. However, assuming it is valid, it predicts a greater boundary restraining effect by smaller particles simply because their combined cross sectional area is greater at a constant volume. If the number of particles remains the same and their effective size increases, as in the present case, Zener's equation predicts a greatly reduced grain size. This is because the effect

Jan 1, 1970

By E. B. Fitch, E. C. Johnson

The operating behavior of liquid-solid cyclones is outlined, together with the nature and range of the process results obtainable, to serve as a background for engineers wishing to consider application of this new process tool. BY now most engineers are familiar with the liquid-solid or Dutch State Mines cyclone. However, it should be helpful to know exactly what it is that the equipment does and what its limits are. Without going into cyclone theory, this paper will describe the operating characteristics of Dutch State Mines cyclones. These are manufactured under license in this country and sold under the trade-marked name of DorrClone. The physical construction of the liquid-solid cyclone has been covered in many papers,'-' the DorrClone in particular being described in some detail by Weems. Fig. 1 shows the unit in cross-section. The feed enters at C. The coarse, heavy particles are thrown centrifugally to the periphery and make their way down the wall to the apex where their rate of discharge as underflow is controlled by an adjustable rubber apex valve. As the apex diameter is decreased the solids build up behind the valve, producing a denser underflow. Meanwhile the fine particles are swept into the upward flowing vortex stream which exits as overflow through the vortex finder, F. Flexibility to produce the specific result desired in a particular process is achieved by providing means for varying the areas of the entrance, vortex discharge, and apex discharge. The entrance area may be varied by insertion of special shims. Vortex discharge area may be changed by use of different-sized vortex finders which are interchangeable. Similarly, the different sizes of apex valves are interchangeable and in addition each apex valve is variable down to about 60 pct of its maximum diameter. A most significant primary distinction to make is that although liquid-solid cyclones have been sometimes called thickeners, they actually are classifiers, and very potent ones. They are almost never thickeners in the special sense that many metallurgical engineers understand the term. There would be no profit in quibbling over the definition of a word, but when the application of cyclones is considered, it will help to understand the difference be- tween two mechanisms, one of which will be called classification, and the other thickening. In what is called thickening the fine solid particles present in the feed hold together by surface attraction during the sedimentation process. The loose network of particles thus held together constrains all particles to settle at approximately the same rate, the larger ones dragging the smaller ones down. As a result, pulp settles with a sharp line of demarcation between solids and a relatively clear supernatant liquid. Essentially all the solids, regardless of their fineness, pass into the thickened underflow, and a clear overflow is separated. In classification, on the other hand, the interparti-cle forces are relatively insignificant as compared to the settling force on the individual particles, and are insufficient to prevent independent movement of the particles. The coarsest, heaviest particles settle most rapidly through the pulp, passing more slowly settling fines. Particles coarser than the mesh-of-separation essentially all settle into the underflow, but if the feed contains any particles finer than the mesh of separation, at least part of them will appear in the overflow. A clear supernatant or overflow can be obtained only if there are no undersize particles present in the feed. Thus it will be seen that classification is impossible under ideal thickening conditions. The finer particles are pulled down at essentially the same rate as coarser particles, and there is no separation on the basis of particle size. The surface attraction holding the particles together in a thickener is usually feeble. Whenever the sedimentation force on any particle is strong with respect to the interparticle forces, that particle can pass through the tenuous structure and settle independently. There are at least four ways of making the sedimentation force strong, with respect to the interparticle forces, and obtaining classification. First, and most obvious, the particles may be large and heavy. Thus coarse sands settle out in a beaker or Dorr thickener ahead of the rest of the thickening solids. Second, the interparticle forces may be altered by physicochemical means; i.e., it is often necessary to add dispersing agents to destroy the interparticle forces and permit classification to take place. Third, the interparticle forces may be reduced by dilution of pulp. It is well known that to obtain the most efficient separation of

Jan 1, 1954

By Robin O. Williams

Robin 0. Williams (Oak Ridge National Laboratory)— The authors have questioned the degree to which the coherency strains between the iron-rich and chromium-rich phases are isotropic as proposed in Ref. 5 on the basis of the difference between the elastic properties of the two phases. The relative magnitude of the stresses is determined by the moduli as shown by Eqs. [2], [3], and [4] of Ref. 34. However, the moduli of the two phases have no direct bearing on the uniformity of either the stress or strain within either phase. The idea that the strains are isotropic within each phase (but normally of different magnitude and always of different sign) is based entirely upon the experimental observation that X-ray line broadening has not been detected even when the particles become rather large. It has not proven possible to grow the particles sufficiently large that they lose coherency. Based upon this lack of line broadening one can estimate an upper limit for the nonuniformity of the strains within each phase as follows. It is considered possible to detect line broadening if it is as great as 10 pct of the separation of the K, doublet for the (211) line using chromium radiation. The doublet separation would correspond to a total strain of 0.0017 such that the total variation of lattice parameter relative to the average lattice is now k0.05x0.0017 or something less than ± * For the present case the strain in each phase is roughly 0.002 such that the variation of strain within a phase will not exceed 5 pct. It is stated that the expression derived for strengthening for the hydrostatic straining as observed in this system would substantially overestimate the magnitude due to dislocation flexure. This is contrary to the conclusion reached in the original paper34 for the present range of particle sizes. What is the lowest temperature at which a has been observed to form in this alloy? M. J. Marcinkowski, R. M. Fisher, and A. Szirmae (nutlzors' reply)— -Williams' arguments based on X-ray findings for a chromium-rich precipitate and an iron-rich matrix strained to a common lattice parameter are certainly convincing. This being the case, there are no shear components of strain associated with the precipitate-matrix aggregate to interact with the shear components of the dislocation stress fields, contrary to the opinion expressed by the present authors. On the other hand, the present authors, in spite of this error, did not expect the shear interactions to be significant. The chief objection to Williams' model in the present case is that the various segments of the dislocation line are assumed to pass from one potential valley to the next independently of neighboring segments. This is only true for a highly flexible dislocation line, i.e., one whose radius of curvature is something less than the center to center distance between precipitate particles which amounts to about 90A in the present alloy. In order to maintain this curvature, an externally applied shear stress of at least 230,000 lb per sq in. would be required or about four times the observed stress. It is therefore concluded that the dislocation lines move rather rigidly through the lattice. This being the case, the forces on the dislocation resulting from the hydrostatic interaction between the stress fields of the edge-dislocation components and the precipitate particles should average out to zero; that is particles above the below the slip plane produce forces on the dislocation of opposite sign and therefore will cancel when averaged over the entire length of the dislocation. On the other hand, since the dislocation is not perfectly rigid, Williams' model may lead to some strengthening, but far less than that predicted. A second and equally serious objective to using Williams' strengthening model for the present alloys is that profuse wavy slip due to the motion of screw dislocations played a predominant role not only in the unaged alloys but in the fully aged ones as well. Since the screw dislocation has associated with it only shear components of stress the hydrostatic strengthening model no longer applies. In view of these arguments the present authors must reject Williams' model of strengthening as being pertinent to the present alloy system. The present authors have made no detailed study of the lowest temperature at which a forms in the quenched ferritic alloys. None was ever observed n the alloys aged at 500°C so that forma-tion must occur at temperatures higher than this and was therefore not a factor in the present study.

Jan 1, 1965

By C. Laird, C. E. Feltner

May different kinds of dislocation structures have been observed in strain-cycled metals and alloys. In order to understand their pattern and causes, an experimental program has been carried out to determine the influence on the dislocation structures of the three variables: 1) slip character of the material, 2) test temperature, and 3) strain amplitude. The results show that at high strain amplitudes cell structures me formed when the slip character is wavy, and that these are progressively replaced by uniform distributions of dislocations as the stacking fault energy is decreased. At lower strains, dislocation debris is formed which consists primarily of dipoles in wavy slip mode materials and multipoles in planar slip mode materials. Temperature merely acts to change the scale of the structure, smaller cells, and clumps of dislocation debris being associated with lower temperatures. It is shown that the results for many metals fit this pattern, which Parallels that occurring in unidirectional deformation. DISLOCATION structures produced by cyclic strain (fatigue) have been examined in a number of metals by transmission electron microscopy. These studies have produced a variety of interesting and often seemingly conflicting results. For example, different investigators have reported such structural features as cells.le4 bands of tangled dislocations,4'5 dense patches or clusters of prismatic dislocation loops, planar arrays,4'10 and various combinations or mixtures of these different structures. Most of these observations have been made on materials which were initially annealed and cyclically strained at low amplitudes resulting in long lives. Recently we have reported observations of the dislocation structures produced in copper and Cu-7.5 pct Al cycled at large amplitudes, resulting in lives of less than 104 cycles.4 These results, examined in combination with those in the literature, have suggested that a common or consistent structural pattern exists. Variations in this pattern appear to be determined chiefly by the three variables, namely, the slip character of the material,4,11 test temperature. and the strain amplitude. To verify this interpretation, we have studied [he influence of the above three variables (in different combinations) on the resultant structures in cyclically strained metals. Copper, fatigued at room temperature, was chosen as a reference state to which all other observations can be compared. The effect of slip character has been investigated by employing fcc metals of different stacking fault energy. Thus aluminum which has a more wavy slip character than copper, and Cu-2.5 pct A1 having a more planar slip char- acter, have been examined. The aluminum samples were fatigued at 210°K thus making their homologous temperature equal to that of copper at room temperature. The influence of temperature has been evaluated by examining the structures in copper at room temperature and 78°K. Finally the effect of strain amplitude was studied by looking at the structures at amplitudes giving lives ranging from 104 to 107 cycles. All of the specimens were examined at the 50 pct life level at which stage the structures have reached a stable configuration.12 I) EXPERIMENTAL PROCEDURE Strip specimens, 0.006 in. in thickness, were prepared from base elements of 99.99 pct purity or greater. Specimens were fatigued by cementing the strips to a lucite substrate which was subjected to reverse plane bending. This method of testing has been described e1sewhere.7 After fatiguing, specimens were thinned and examined in a Philips EM 200 which was equipped with a goniometer stage capable of ±30-deg tilt and 330-deg rotation of the specimen. On the basis of separate calibrations,13 allowances were made for the relative rotation and inversions between the bright-field images and the diffraction patterns. II) RESULTS AND DISCUSSION The life behavior of the materials under different test conditions is shown in Fig. 1 in the form of plots of total strain range vs cycles to failure. Comparisons of structures produced in the different materials were made at amplitudes which produced equal numbers of cycles to failure. The influence of strain amplitude on the structures produced in the reference state material (copper tested at room temperature) is shown in Fig. 2. At the 104 life level the structure produced comprises cells similar to those previously observed.3,4 They are approximately 0.5 p in diam and the cell walls are generally more regular or sharper than those produced by unidirectional deformation.14 At the 10' life level the

Jan 1, 1969

By M. J. Marcinkowski, A. S. Sastri

A detailed compressive stress-strain analysis and transmission electron microscopy investigation has been made of the deformation behavior occurring in a 50 at. pct Ni-Ti (hypoeutectoid) alloy and a 54.5 at. pct Ni-Ti (hypereutectoid) alloy. In the case of the hypoeutectoid alloy, three stages of work hardening are observed. Stage I occurs at a very low stress and is associated with plastic deformation via martensite formation. Stage 11 is characterized by very rapid work hardening and is due to difficulties in causing further deformation in the fine martensite aggregate produced in Stage I. Stage III which occurs at very high stress levels is characterized by smaller work hardening rates and is due to the plastic deformation arising from alternate reconversions of the original martensites to martensites of varying orientation. Rapid quenching of the hypereutectoid alloy leads to very high yield strengths and is related to a fine precipitate dispersion that such treatment brings about. The present investigation represents the final phase of a three-part study directed toward an understanding of the solid-state transformations in near equi-atomic Ni-Ti alloys as well as the deformation mechanisms associated with these alloys. In the first part,"2 to be henceforth referred to as I, it was found that alternate simple shears on {112} planes and in (111) directions convert the parent B2 structure in the equiatomic NiTi alloy into two distinct close-packed monoclinic martensites. All of the marten-sites were of this type, whether they were formed by cooling or by plastic deformation, whether induced to form in bulk samples or in thin foils, or whether examined in the electron microscope at room temperature or below. On the other hand, in the second part of this investigation,3 to be reffered to as 11, it was shown that upon slow cooling to about 640°C. alloys in the neighborhood of NiTi which possess the B2 structure transform eutectoidally into their equilibrium phases Ti2Ni and TiNi3. However, preceding the formation of these equilibrium phases a series of metastable intermediate phases are formed. This paper will set as its goal the elucidation of the remarkable deformation behavior exhibited by NiTi. In particular, Buehler and Wiley4 have found equiatomic NiTi to be surprisingly soft, while Buehler et al.5 have shown this alloy to possess a memory effect: i.e., upon bending at room temperature it will revert to its original shape when heated to above about 50°C. In I it was shown that NiTi was soft in the sense that the yield stress was low; nevertheless, the alloy work-hardened at an extremely rapid rate to very high stress levels. On the other hand, the hypereutectoid alloys with somewhat higher nickel, say 54.5 at. pct (60 wt pct) have enormously increased yield strengths compared to those of the equiatomic alloys. In order to determine the atomistic processes giving rise to the above behavior, it was decided to examine samples that were wafered from bulk specimens deformed in compression to various strains using the techniques of transmission electron microscopy. EXPERIMENTAL TECHNIQUE All of the alloys used in the present investigation contained either 50 at. pct Ni (55.06 wt pct) or 54.5 at. pct Ni (60 wt pct) and were arc-melted in the form of a finger using the same techniques described in I and II. The finger was capsulated in a stainless-steel jacket and swaged at 850°C into rods. Compression specimens 0.300 in, long and 0.200 in. in diam were machined from these rods. In order to completely re-crystallize the samples and remove residual stresses, all of them were capsulated in evacuated quartz, annealed for 1/2 at 1050°C. and then furnace-cooled. Compression tests were carried out in an Instron tensile testing machine covering a range of temperatures from —196° to 200°C using procedures described previously.6'7 In all cases crosshead speed was 0.02 in. per min. Wafers 0.015 in. thick were spark-cut from the cylindrical samples at 45 deg to the compression axes after they had been deformed to the desired strain. These specimens were then spark-planed to about 0.005 in. and then electrochemically thinned for examination by transmission electron microscopy as described in I.

Jan 1, 1969

By V. M. Karve, K. K. Majundar, K. V. Viswanathan, J. Y. Somnay

The effect of calcium, magnesium, iron (both ferrous and ferric) and aluminum ions, which are commonly encountered in a typical beryl ore, was studied in the flotation of pure beryl, soda-feldspar and quartz. The vacuumatic flotation technique was employed. With sodium oleate as collector and in the absence of any activator, beryl floated in a pH range of 3 to 7.5, whereas feldspar and quartz did not float at any pH up to 11.5. The pH range of flotation increased in the presence of the ions studied. With calcium and magnesium ions beryl floated from 3 to 11.5 pH and beyond, soda-feldspar floated beyond pH 6 and quartz floated beyond pH 8. Ferrous ion activation was found to be similar to that of calcium and magnesium. Activation by ferric and aluminium ions was found to be complex and the lower and upper critical pH for all the three minerals was around 2 and 10 respectively. These studies indicated the possibility of separation of beryl from feldspar and quartz even in the presence of calcium, magnesium and ferrous ions between pH 4 and 6. Flotation tests on a mixed feed of pure minerals in a 10 g cell revealed that beryl can be selectively floated from feldspar and quartz if ferric ion is reduced to ferrous state or if it is complexed. Beryl occurs mostly in pegmatites, and hence is associated with feldspar, quartz and micas and small amounts of other minerals such as apatite and tourmaline. The separation of beryl from these minerals is difficult because all the silicates accompanying beryl have more or less the same physical properties. Specific gravities of beryl, feldspar and quartz are 2.70, 2.56 and 2.66 respectively. Electrostatic separation has been suggested but no work has been reported. ' The adsorption of sodium tri-decylate tagged with Cl4 on beryl, feldspar and quartz reveal similarity in surface properties. Much work has been reported on the flotation of beryl from ores, either directly or indirectly as a by-product, but little is known about the fundamental aspects of beryl flotation. Kennedy and O'Meara3 laid emphasis on prior cleaning of the mineral surfaces with HF. Mica is removed first by flotation of beryl with oleic acid, around neutral pH. Runke4 introduced calcium hypochlorite conditioning in a final separation stage for activating beryl in a mixed beryl-feldspar concentrate, and after washing to remove the hypochlorite, floated beryl with petroleum sulphonate. The Snedden and Gibbs5 procedure is somewhat similar to that of Kennedy and O'Meara. Emulsified oleic acid is used as collector. Recently Fuerstenau and Bhappu6 studied the flotation of beryl, feldspar and quartz with petroleum sulfonate in the presence of activators and stressed the importance of iron in the flotation of beryl. From the studies conducted in this laboratory, it was found that feldspar and quartz as such do not float with sodium oleate, but in practice selective flotation of beryl from feldspar and quartz in an ore is found to be impossible with sodium oleate as collector. A glance at the chemical analysis of typical beryl ore indicates the presence of several ions like Ca ++, Mg++, Al + + + and Fe+++ in abundance and Ti++++ and Mn++ in traces. Hence, in an attempt to explain the behaviour of feldspar in the beryl flotation, the effect of Ca++, Mg++, Al+++ and Fe+++, which are known as gangue mineral activators7'8 has been investigated. Materials and Methods: Lumps of beryl ore (hand picked) were boiled with 10% sodium hydroxide and washed with distilled water. They were further boiled many times with 10% hydrochloric acid till no positive test for iron was obtained with ammonium thio cyanate. This was followed by thorough flushing with double distilled water. The lumps were crushed in a porcelain mortar and pestle under water. The minus 65 + 100 mesh fraction was used for testing and was always stored under distilled water. Pure feldspar and quartz were similarly prepared and the minus 65 + 100 mesh fractions collected. Inorganic ions tried as activators were ca++, Mg++ , Fe++, Fe ++ and A1 +++ . Calcium nitrate, magnesium chloride, ferrous ammonium sulfate, ferric ammonium sulfate and aluminum nitrate of G.R.E. Merck grade were used. B.D.H. technical grade sodium oleate was used as a collector. The vacuumatic flotation technique developed by Schuhmann and Prakash was used for studying the effect of pH on flotability. 7 The indications given by this work were confirmed by using 10 g miniature cell.'

Jan 1, 1965

By Norman Lamont

The evaluation of certain reser-voir properties, such as porosity and fluid saturation, from electrical well surveys has been widely accepted in petroleum engineering. Various investigators have established relationships between these properties and certain parameters which affect the response of the electrical log. Among these are the resistivities of the mud, its filtrate, and its filter cake. In 1949, Patnode1 established a relationship between the resistivities of the mud and filtrate. The well logging service companies have contributed relationships for the mud-mud cake resistivities2,3 These have been valuable since it was the practice to measure only resistivity of mud at the well site. During the mid-1940's the industry began drilling wells with oil-emulsion drilling fluids. These were conventional aqueous muds with a dispersed oil phase. Since 1950, oil-emulsion muds have been used on an increasing number of wells each year. However, the practice of measuring only the resistivity of the mud at the well site has continued, and the mud filtrate and mud cake resistivities have been determined by the above-mentioned relationships. Service companies are now equipped to measure all three resistivities at the well site. An investigation was conducted on the resistivities of oil-emulsion muds, mud filtrates, and mud cakes to determine if these values conformed to the relationships for aqueous muds. TYPES OF MUDS Fifty-one oil-emulsion mud samples were prepared in the laboratory following a standard manual' published by a leading mud company. The diesel oil in the samples varied from 5 to 50 per cent, the majority of the samples being in the 10 per cent region. The basic aqueous mud types which were converted to oil-emulsion muds were commercial clay and bentonite muds, low pH and high pH, caustic-quebracho treated muds, and lime treated muds. The emulsions were stabilized by dispersed solids, lignins, lignosulfo-nates, sodium carboxymethyl cellulose, or sulfonated petrolatum. It is worthy of note that after a quiescent period of two weeks at room temperature all samples, regardless of emulsifying agent, remained stable. The make-up water for the muds was from the laboratory tap. Resistivities were varied by the addition of table salt to the water. A range of mud resistivities from 0.44 to 3.9 ohm-m was obtained in this way. Twenty-three field muds were tested. These covered the same range of mud types as did laboratory muds. Oil provinces of the Gulf Coast, South Texas, West Texas, Oklahoma, Montana, and Canada were represented. MUD TEST PROCEDURE Each mud was tested for density, viscosity, pH, and filter loss by standard testing techniques. The resistivity measurements were obtained with a Schlumberger EMT meter. This meter required small volumes of sample, e.g., 2 mm. Filtrate was obtained from a Standard Baroid fil-ter press at the end of a 30-minute test. The filter cake from the same test was used for cake resistivity measurements. Mud, filtrate, and cake samples were heated to 100" F in a constant temperature water bath prior to measurement of resistivities. RESULTS The relation between mud resistivity (Rm) and mud filtrate resistivity (Rmf) is shown in Fig. 1. The solid line represents an average for the data. The equation of this line is Rmf =0.876 (Rm) 1.075 . . (1) Arbitrary limits, indicated by the dashed curves, have been set. The majority of the data falls within these limits, but some points do lie outside the limits. The approximate equation Rmt = 0.88 Rm , . . . . (2) will give satisfactory results within these limits. The data on mud cake resistivity Rmc is shown in Fig. 2. The solid line is an average for the data. The equation for the line is Rmc = 1.306 (Rm)0.88 The dashed lines are arbitrary limits on the data. Within these limits, Eq. 3 may be simplified to Rmc = 1.31 Rm . . . . (4) DISCUSSION The limiting curves in Figs. 1 and 2 represent maximum deviations of ±25 per cent. Thus the use of the average curves can introduce considerable error. There is no substitute for accurate measurements of mud, mud cake, and mud filtrate resistivities at the well site. The mud sample tested should be representative of the mud opposite the formation being logged. The average mud filtrate resistivity curve of Fig. 1 is reproduced in Fig. 3 with two curves which have been published for clay-base aqueous muds2,3. The latter curves were determined from average values of a large number of drilling fluids. The three curves have essentially the same slope and the differences between them are from 7 to 22 per cent. Comparison is made only to illustrate the possibility of error

Jan 1, 1958

By B. Ramaswami, U. F. Kocks, B. Chalmers

The latent hardening of silver and an Ag-Au alloy was investigated by lateral compression, overshoot in tension and cormpression, and the stability of multiple-slib orientations. The latent hardening of a secondary slip systenz depends on its relation to the primary slip system. For most secondary slip systems the latent hardening is larger for Ag-10 at. pct Au than for pure silver. The maximum increase in. flow stress on a secondary slip system over that of the primary slip system was 40 pct. The work hardening during the lateral-compression test on the latent system after prestress on the primary system is iuterbreted in terms of the preferential distribution of barriers to dislocation movement with respect to the active slip system in work-lzardened fcc crystals. The work-hardening in fcc crystals is mainly due to the dislocation interactions and the barriers to dislocation movement formed as a result of reactions between dislocations of different slip systems. The operation of sources on the latent system depends on the flow stress of those systems; hence, the increase in flow stress of a latent system due to glide on an active system, which is called latent hardening, is an important element in understanding the phenomenon of work hardening. The problem of latent hardening has attracted the attention of many investigators in the past. For example, a theoretical study of the elastic latent hardening of the latent systems due to glide on an operative system has been made by Haasen' and ~troh. These calculations, however, neglect the stress required for the intersection of forest dislocations by the glide dislocations, a factor which would be important for producing macroscopic strains on the secondary slip systems. The importance of this factor will become evident from the results presented here. Attempts have also been made to determine the latent hardening of different slip systems by experimental means by the methods summarized in Table I.3-9 The experimental methods used have been subject to certain limitations. For instance, in the method used by Hauser,9 frictional constraints between the specimen and the compression platen were not eliminated by proper lubrication (see Hos- ford10). Secondly, with the exception of Kocks,6 Hauser,9 and Rohm and Kochendorfer,11 latent-hardening studies have been made on only one of the slip systems, i.e., on either the conjugate or the coplanar slip system; hence, extensive results are not available on the latent hardening of different slip systems in the same materials, with the exception of aluminum.6 It was therefore decided to study the latent hardening of the conjugate, critical and half-related slip systems in silver. Similar experiments were done in Ag-10 at. pct Au to study the effect of solute (gold) on the latent hardening of silver. Lastly, indirect evidence can be obtained by a study of the orientation stability of crystals of multiple-slip orientations in tension and compression. This method has been used by Kocks6 to supplement his studies of latent hardening in aluminum. Similar studies were made at room temperature in single crystals of silver. EXPERIMENTAL PROCEDURE The single crystals of the desired orientations were grown and the tensile test specimens were prepared as described in Ref. 12. The compression tests were made on 1/4-in.-cube specimens. The specimens were cut from single crystals, in the Servomet spark-erosion machine.13 The two cut surfaces were planed using the lowest available planing rate in the machine to minimize the deformation layer. A brass strip was used as the planing tool. This method of preparation ensured plane parallel faces for the compression tests. The deformed material was removed by prolonged etching in a weak etching solution. A weak etching solution was used to prevent pitting of the surfaces and to ensure uniform etching. About 25 to 50 µ of material were removed from all faces by the etching treatment. The specimens were then annealed for 24 hr at 940°C in oxygen-free helium and cooled in the furnace to room temperature over a period of 7 hr. After annealing, the orientation of the specimens was determined by Laue back-reflection technique to make sure that no recrystallization had occurred on annealing. The compression-test technique and setup are described in Ref. 14. The Laue back-reflection technique was used to study the overshoot in tension, the overshoot in compression, and the stability of the axial orientation in tension and compression. The tests were interrupted after every few percent strain to determine the axial orientation. In investigating the overshoot in compression, the operative system was determined by studying the asterism of the Laue spots.

Jan 1, 1965

By K. T. Aust

It is proposed that the intergranular corrosion of austenitic stainless steels is associated with the presence of continuous grain houndary paths of either second phase, or solute segregate resulting from solute-vacancy interactions. Experimental observations of structural changes and crrosion behavior of different types of austenitic stainless steel provide support for this poposal. On the basis of this model, it is shown that the intergranular -corrosion susceptibility of austenitic stainless steels in nitric-dic hromate solution may be substantially reduced either by suitable heat treatments or by impurity control. AUSTENITIC stainless steels, such as Type 304, generally have excellent corrosion resistant properties when properly solution heat-treated and used at temperatures where carbide precipitation is slow. However, several corrosion environments have been found which produce intergranular corrosion of solu-tion-treated stainless steels, that is, those steels with no detectable carbide precipitation.''2 Of the various corrosion environments, the most widely used test solution has been the boiling nitric-dichromate solution. In these acid solutions, stainless steels have been found to be susceptible to intergranular attack despite the addition of carbide-forming elements such as titanium or columbium, or despite lowering of the carbon content or use of high-temperature solution treatments. Studies of the electrochemical mechanism of corrosion attack have been made by several worke1s3'4 who found that oxidizing ions such as crt6 depolarize the cathodic reactions and consequently raise the open-circuit potential of stainless steel immersed in nitric acids. As a result of this, the anodic reaction is accelerated. The reason for the localization of anodic activity at the grain boundaries, and resulting intergranular corrosion, has not been conclusively determined. Several workers, e.g., Streicher,3 and Coriou et al.,4 have suggested that the strain energy associated with grain boundaries provides the driving force for the accelerated intergranular corrosion. This argument would predict that alloys of high purity would still be susceptible to intergranular attack. However, work by chaudron5 and by ArmijO,6 has shown that high-purity alloys are immune to attack, in disagreement with this argument. An alternative suggestion is that chemical concentration differences exist between grains and grain boundaries, that is, impurity segregation at boundaries, and that these chemical differences provide the driving force for localized attack. It is this impurity segregation which can lead to accelerated dissolution of grain boundaries when the alloy is exposed to a suitable corrodant. This mechanism would predict the immunity of high-purity alloys to inter-granular attack, which is in agreement with experi-mental observations. In the present paper, some recent studies on inter-granular corrosion of austenitic stainless steels which were conducted by coworkers and myself will be re-tibility A simple model will be described in which it is proposed that the intergranular corrosion of aus-tenitic stainless steel is associated with the presence of continuous grain boundary paths of either second phase or solute-segregated regions.* On the basis of this model, it is suggested that the intergranular corrosion rate can be markedly reduced by the formation of a discontinuous second phase at the grain boundaries if the discontinuous second phase incorporates the major part of the segregating solute, drained from the grain boundary region. Results are presented of corrosion tests and electron microscopic studies of different types of austenitic stainless steel after various heat treatments which provide experimental support for this model. Finally, a solute clustering mechanism, based on a solute-vacancy interaction, is shown to be consistent with the results obtained for inter-granular corrosion of solution-treated austenitic stainless steels. EXPERIMENTAL Corrosion tests using weight loss measurements were made on sheet specimens, which were lightly electropolished, washed, and immersed in boiling (115°C) 5 N HN03 containing 4 g crt+6 per liter added as potassium dichromate. Studies in which the inter-granular penetration depth was measured both by electrical resistance and metallographic methods have shown an empirical correlation between the rate of intergranular penetration and the weight loss per unit time for identically treated specimens of stainless steel." As a result, although all the corrosion data reported here are in terms of simple weight loss measurements, these data are considered to reflect primarily the rate of intergranular dissolution. Fig. 1 shows a typical result of intergranular attack of a solution-treated Type 304 stainless steel after 4 hr in a boiling nitric-dichromate solution. The wide grain boundary grooving at the surface, and the attack at incoherent twin boundaries, are evident; very little corrosion attack is seen at the coherent twin boundaries. INTERGRANULAR CORROSION MODEL

Jan 1, 1970

By D. Y. F. Lai, R. J. Borg

Tracer diffusion of Fe59 has been measured in the a-stabilized Fe-1.8 at. pet V alloy from 700° to 1500°C. The activation energies are obtained in both the presence and absence of magnetic order. Furthermore, it is established that diffusion in the alloy is identical to that in pure iron and consequently the values of Do and Q accurately represent the temperature dependence for self-diffusion. The purpose of this investigation is to obtain an accurate estimate of the temperature dependence for self-diffusion in bee iron in both the presence and absence of magnetic order, and, in so doing, to establish the temperature range of the magnetic effect.&apos;" As the temperature interval suitable for diffusion measurements is severely limited in both bee phases of pure iron because of the intervening fee ? phase, the experiments were performed on an a-stabilized alloy containing 1.8 at. pet V. This alloy is bee over the entire range from room temperature to the melting point. Although there have been several independent investigations of self-diffusion of iron in a, iron,1, 3-6 there still exists considerable disagreement regarding the values of Do and Q for the paramagnetic region. The two systematic studies of diffusion in 6 iron6, 7 previously reported are also only in fair agreement; but in view of the extremely small temperature range available for diffusion studies, i.e., 1390o to 1535oC, this is not surprising. It is comparatively easy to obtain accurate values of Do and Q for the a-stabilized alloy inasmuch as measurements can be made over the entire temperature range -700o to 1500°C. However, in order to assume that these same values apply to pure iron requires careful comparison of the data in the a, and 6 regions in both the alloy and pure iron. We have made several measurements in the appropriate temperature ranges and are unable to establish any systematic difference between the diffusion coefficients of iron in pure iron and in the alloy. We therefore conclude that the values obtained for the alloy are truly applicable to pure iron; the complete evidence favoring this conclusion will be discussed later in this paper. EXPERIMENTAL The experimental methods will be given here only in barest detail since they have been thoroughly de- scribed elsewhere.l, 7 The alloy was prepared by induction melting and chill casting under argon. Diffusion samples were machined from the ingot and annealed in hydrogen for several days at 900°C to give an average grain diameter of 1 to 2 mm. The penetration profiles of the tracer were established by a sectioning technique, the residual activity being counted after the removal of each section. The tracer used is Fe59 which emits two high-energy ? rays of 1.098 and 1.289 Mev, respectively; these were detected by a ? scintillation counter equipped with a pulse-height analyzer. For the measurements in the temperature range -700o to 1130°C the samples were vapor-plated with Fe59, encapsulated in quartz under vacuo, and annealed in resistance-heated furnaces which are controlled to ±1°C. The specimens diffused at higher temperatures are prepared as edge-welded couples, the two halves being separated by a thin washer of the alloy to prevent sintering. The diffusion anneal is then carried out by inductive heating under a dynamic vacuum. The temperature is monitored pyrometrically. RESULTS The diffusion coefficients are obtained from the penetration profiles in the usual way using the error-function complement relationship. The results over the entire temperature range are shown in Fig. 1. In the linear region, 900o < t > 1500°C the least mean squares (lms) values of the diffusion coefficients are given by D = 1.39 exp[-(56.5 ± 1) x 103/Rt] cm2/sec [l] The average departure of the measured diffusion coefficients from the values given by Eq. [1]In order to determine whether or not the slope is truly constant over the entire range from 900" to 1500°C, the data are arbitrarily divided into two groups, the first containing values between -900" and 1133°C and the second between -1133o and 1500°C. The lms values for the two groups are given by Eqs. [2] and [3]: D = 0.519 exp[-55.7 x 103 /RT](900° to 1133°C) cm2/sec [2] D = 1.45 exp[-56.7x103/RT] (1133° to 1500=C) cm2/sec [3] Thus, there is no significant difference between the high- and low-temperature segments of the linear region. This not only assures us of the consistency of the values obtained by induction heating as compared to those obtained from the resistance-heated

Jan 1, 1965

By G. H. Turner, R. C. Bell, E. Peters

Zinc oxide activities in a typical lead blast furnace slag have been calculated from plant operating data. These activities were used to assess the probable effect of fuel composition, oxygen enrichment, and air preheating on the efficiency and capacity of the slag-fuming operation. THE physical chemistry of zinc fuming has been examined with three objectives in mind: 1—to predict conditions favorable to increasing furnace capacity, 2—to predict the changes required to fume zinc more economically, and 3—to explain reported differences in the efficiencies of various slag-fuming plants. This study, made at ail in the plants and laboratories of The Consolidated Mining and Smelting Co. of Canada Ltd., developed from a program undertaken some three years ago on behalf of the AIME Extractive Metallurgy Div. subcommittee on slag fuming. Lead metallurgists first became interested in the recovery of zinc from lead blast furnace slags in 1905 and 1906. An excellent review of the early experimental work has been made by Courtney,&apos; who described blast furnace, reverberatory furnace, and converter methods of fuming zinc from slag. Some of the investigators did not appreciate the importance of reducing the zinc oxide content of the slag to metal in order to fume it, since they tried compressed air blast without fuel in their earliest attempts. However, by 1908, the importance of reducing the zinc was established.&apos; In 1925, the Waelz process for the recovery of zinc oxide from oxidized zinc ores was developed in Germany.&apos; This process was not readily adaptable to lead blast furnace slags because of the difficulty in handling fusible charges in a kiln. What appears to have been the first slag-fuming operation as it is known was commenced by the Anaconda Copper Mining Co. at East Helena, Mont. in 1927." The first Trail furnace was completed in 1930, and this was followed by the construction of several other slag-fuming plants. During the period in which slag fuming has been extensively employed, little development of the chemistry of this process as a whole has taken place. Several good papers on the petrography of lead blast furnace slags have been published,""= but these studies could do little more than establish the forms in which lead and zinc occur in the initial charge and final products of the slag-fuming operation. In recent years, zinc-smelting problems have been ap- proached from a thermodynamic point of view. Maier has published an excellent thermodynamic treatment of zinc smelting." The important thermodynamic properties of zinc and its compounds have been determined and checked by other investigators.&apos; However, to the best of the authors&apos; knowledge, no thermodynamic treatment of the fuming of zinc from slag has been published. A thermodynamic study of any process requires that the essential chemistry of that process be known. In slag fuming there appear to be some differences of opinion as to whether the active reducing agent is elemental carbon or carbon monoxide. Furthermore, some observers have noted that high volatile coals appear to be more efficient than low volatile coals, indicating that hydrogen is also an important factor in the reducing efficiency of a fuel. That both hydrogen and carbon monoxide are effective reducing agents for the zinc oxide content of lead blast furnace slags can be demonstrated readily by introducing these gases into a slag bath held in a neutral vessel at 2100°F (1150°C). Elemental carbon also will reduce zinc oxide, but it is improbable that much free carbon is available for reduction of zinc, as the reaction between the finely powdered coal and air should be largely completed before the solid coal particles reach the slag. Some large-scale fuming experiments using gaseous hydrocarbons have been carried out by other investigators, but, as far as is known, these have not been developed yet into operating processes. The thermodynamic treatment in this paper is based on the following reactions: 1—to supply the thermal requirements C+V2O2- CO [1] C + 0,-CO, [2] H2+ ~z0,-H,O 131 and 2—to reduce ZnO ZnO + CO + Zn + CO, c41 ZnO + H, e Zn + H,O. [51 The furnace-gas composition also is controlled by the equilibrium constant of the familiar water-gas reaction H,O + CO + CO, + H2. C6l In order for the thermodynamic calculations to be quantitatively applicable, it is necessary that the chemical reactions to which they are being applied

Jan 1, 1956

By F. E. Pawlek, J. K. Gerlach

The chloridizing roasting of ores is applied when metal sulfides and oxides are to be converted into soluble or volatile compounds. The chlorine required is either obtained from the admixed chlorides of sodium or calcium or added in the gaseous state. In the first part of the investigations the reaction rate of the chlorides of sodium or calcium with gas mixtures of SO,-0, or SO ,-O2 ,-SO , was measured. The rate for reactions with gas mixtures SO2-O2 is ThE chloridizing roasting of ores is applied when metal sulfides and oxides are to be converted into soluble or volatile compounds. At present the process is mainly applied to produce nonferrous metals which occur in pyrite cinders in small concentrations. Thereby the nonferrous metals are converted into water-soluble, acid-soluble, or volatile compounds whereas all the iron remains as insoluble oxide. The chlorine required is either obtained from the admixed chlorides of sodium or calcium or added in the gaseous state. The reactions occurring during the roasting process can be divided into two groups: solid-solid reaction and gas-solid reaction. The reactions between solids proceed by means of solid-state diffusion and are therefore of low velocity. The heterogeneous reactions between solids and gases of the roasting atmosphere5 are high-velocity processes and determine the velocity of the chloridizing roasting. These gas-solid reactions shall be the subject of the paper presented. In order to investigate the still little-known processes which occur during the chloridizing roasting 6-&apos; the complex reaction is split into several partial steps. First the reactions of NaCl and CaCl, with gas mixtures of SO2 and 0, have been investigated at temperatures between 500" and 600°C by measuring the weight increase of the samples. The gas mixtures used in this series of experiments had first variable compositions, then the amount of SO 2 had been increased. Furthermore the influence of Fe 2 O3 admixtures upon these reactions, the behavior of pure Fe 2 O3 with the gaseous reactants, and the chlorination of the sulfides of lead, copper, nickel, and zinc have been investigated. FORMATION OF GASEOUS CHLORINE Pyrite cinders are never completely roasted and therefore contain still a small amount of sulfide sulfur. When heated again in air, this sulfur is converted into SO,. Accordingly the formation of chlorine can first be described by the reactions: dependent on the composition of the gas phase. If more than 1 pct SO 3 is added to the roasting gas, the reaction rate is determined only by the concentrations of the SO,. In the second part the reactions between chlorine and metal sulfides are discussed. The rate of formation of gaseous chlorine is higher by me order of magnitude than is the reaction rate between ZnS and chlorine. The reaction rate of NiS and PbS lies considerably below that of ZnS. The conversion rate of both pure Fe 2 O 3 and Fe 2 O 3 containing NaCl or CaCl2 when reacting with SO2-O2, mixtures with and without SO3 portions was measured at temperatures of 500", 550°, and 600°C. The weight increase of pressings was determined by means of a spiral balanceg and the reaction rate calculated therefrom according to Eqs. [ll to [31 and [5] to [7]. The prepared samples were suspended on a platinum filament in a vertically mounted tube of mullite (ID 4 cm, length 110 cm) which could be heated by a resistance tube furnace. The platinum filament was tied to the lower end of the spiral balance. A supremax glass tube (length 70 cm) was mounted gas-tight on top of the reaction tube. The unit was sealed up at its top by a ground-in stopper which was holding the spiral balance with the sample. The spiral balance therefore hung outside the high-temperature region of the furnace. Fig. 2 shows the experimental arrangement schematically. While lowering the sample into the reaction tube pure nitrogen was flowing through the reaction zone providing a protective atmosphere. After the sample had reached the reaction temperature within approximately 1 min, the protective gas was replaced by the sulfur dioxide-oxygen reaction mixture. It took about 30 sec until the mixture filled the tube homogeneously. A Ni/NiCr thermocouple placed in the center of the furnace where the sample hung during the measure-

Jan 1, 1968

By J. K. Stanley

Knowledge of the diffusivity of carbon in the low temperature form of iron (alpha iron existing below 910°C) is at the moment of considerable interest in the study of the decomposition of austenite and martensite, the elastic after-effect,123 the magnetic after-effect4 and the decarburization of steel below 910°C. Information on the solubility of carbon in iron, and to a lesser extent its diffusion, is also important in consideration of such phenomena as blue-brittleness, temper-brittleness, "magnetic" aging, quench-aging, strain-aging, and possibly the yield point. In order to obtain more information on these subjects more fundamental knowledge is necessary. It is the purpose of this work to present data on the diffusion and solubility of carbon in the alpha iron. The high temperature form of iron (gamma; face-centered cubic) existing above 910°C is capable of dissolving relatively large amounts of carbon, up to 1.7 pet at 1130°C, while the low temperature form (alpha, body-centered cubic) existing below 910° dissolves only a limited maximum amount of less than 0.02 pet carbon at 725°C, according to data obtained here. Since the solubility of carbon in the face-centered or gamma iron is large, relatively speaking, no great analytical difficulties have been encountered in the determination of the solubility lines5 or of the diffusion of carbon.0 The limited solubility of carbon in alpha iron offers difficulties because experimental procedures and analytical methods for low carbon contents below say 0.01 pet have to be more refined than techniques used for work with gamma iron. Because of the difficulties of applying conventional methods to the determination of the diffusion of carbon in alpha iron, virtually no work has been done on this subject. However, by proper refinement of the analytical method for small amounts of carbon, the determination of the diffusion coefficient can be made readily using modified procedures. The solubility of carbon in alpha iron has been determined over a temperature range by various investigators, but the agreement among them is poor. The present investigation establishes the limits quite accurately. Information of this kind is useful in establishing the correctness of equilibrium diagrams but, more significantly, such information on maximum solubilities, especially when extended to alloyed ferrites, should be extremely important in the study of aging and related phenomena. Literature The literature existing on the diffusion, in particular, and on the solubility of carbon in alpha iron is not extensive. The data which exist are not of a high order of accuracy, much of them being in the realm of conjecture. THE DIFFUSION OF CARBON IN ALPHA IRON Whiteley7 made the qualitative ob- servation, using metallographic techniques, that the rate of diffusion of carbon at the A1 (725°C) point was very rapid and that its diffusion was still rapid at 550°C. Snoek,4 studying the magnetic aftereffect in high purity iron, arrived at the conclusion that the after-effect could be explained by the presence of small amounts of carbon diffusing under the influence of magnetostrictive strain (lattice distortion due to magnetic interaction). In later work, Snoek8 made an estimate of the ratio of carbon diffusion in alpha to its diffusion in gamma iron, and concluded that for a temperature of 910°C the ratio of Da/D? was 2600. Polder,9 basing his calculations of D on relaxation phenomena in the elastic after-effect, estimated that Da is about 1/3 of D? at 910°C (1183°K) and is about 1/12 of Dy at 727°C (1000°K). Polder&apos;s equation for the diffusion of carbon in alpha iron was calculated to be 18000 D = 5.2 X 10-4 e-RT cm2 per sec Ham10 obtained data for the diffusion and solid solubility of carbon in alpha iron at two temperatures by using one technique similar to that employed in this study. He found a D of 8.0 X 10-7 cm2 per sec at 702°C and of 2.7 X 10-7 at 648°C. THE SOLUBILITY OF CARBON IN ALPHA IRON Although pearlite is absent in steels containing 0.06 pet,11 0.05 pet,12 or 0.045 pet C,13 it appears that the carbon in these steels cannot be in solution in ferrite. The solubility of carbon at the A1 (725°C) point was first determined by Scott14 on the basis of cooling curves, and was found to be between 0.03 and 0.04 pet C. Tamura15 by interpolating between the solubility of carbon in delta iron at 1400°C and in alpha at room temperature (assuming zero solubility) ar-

Jan 1, 1950

By A. L. Mincher, W. F. Sheely

Mechanical properties of columbium have been studied over the temperature range of -196 to 1093oC. The decreased strengthening influence of cold-work at temperatures below ambient has been interpreted in terms of the Peierls-Nabarro effect. Maxima in the rate of strain hardening observed during tensile testing in the range 250-600°C. have been correlated with interstitial impurities to indicate the temperature ranges at which carbon, oxygen, and nitrogen, respectively, are responsible for strain aging. THE growing need for structural materials for use above the useful service temperatures of the iron-, nickel-, or cobalt-base alloys has caused the refractory metals to be considered as potential engineering materials. These metals, which include columbium, tantalum, molybdenum, and tungsten, are called refractory because the lowest melting point among them,that of columbium, is about 1000°C higher than the average melting temperatures of conventional high-temperature alloys. They are all body-centered cubic transition metals and, as such, their mechanical properties have basic characteristics which distinguish them from the face-centered cubic metals. For example, all show a much steeper rise in strength with decreasing temperature below room temperature than do the face-centered cubic metals, and their mechanical properties are strongly influenced by interstitially dissolved impurities. In order that these new metals may be used efficiently, it is necessary that their characteristics of behavior be fully known. In this paper, the mechanical properties of columbium will be examined over a wide range of temperatures. In particular, the influences of cold-work and individual species of interstitial impurity atoms on mechanical properties will be described, and basic mechanisms which may control the observed characteristics will be explored. EXPERIMENTAL The material used in this investigation was Union Carbide Metals Co. columbium roundels consolidated to four 4-in. diam ingots, three by consumable-electrode arc melting and one ingot by electron beam melting. Impurity contents of the ingots and methods of ingot conversion and treatment are summarized in Table I. The only metallic impurity occurring in any significant quantity was tantalum at about 0.1 pct. Iron, silicon, titanium, and zirconium were each less than 0.015 pct; boron was 1 ppm or less. This should have no appreciable influence on properties. The electron beam melted material, being the purest, will be used as the basis for comparison in the discussions to follow. Tensile tests were conducted from-196 to 1093oC, on both cold-worked and fully recrystallized arc-melted and electron-beam melted columbium using standard 1/4-in. diam, 1-in. long gage length test specimens. A strain-rate of 0.005 in. per in. per min was employed until the 0.2 pct yield strength was achieved and then the strain-rate was increased to 0.05 in. per in. per min for the balance of the test. Samples were protected in an inert atmosphere at tests above 300°C. The tensile properties obtained on the electron-beam melted columbium, E, in both the cold-swaged and recrystallized conditions are given in Fig. 1. The yield strength data of Dyson, et al.,&apos; obtained on recrystallized electron beam melted columbium and the tensile strength data reported by Tottle2 on powder metallurgy columbium are included in Fig. 1. The material used by Tottle had been purified by vacuum sintering. There is excellent agreement between Dyson&apos;s data and those obtained in the present investigation. The tensile strengths obtained by Tottle were slightly greater than those obtained in this investigation on electron-beam melted columbium but varied with temperature in a similar manner. Tottle&apos;s data showed a maximum in tensile strength near 500°C, as did our data on electron-beam melted material, and also showed a small maximum at 300°C. The significance of these maxima will become evident later in the discussion. The tensile properties of cold-swaged and recrys-tallized arc melted columbium are plotted in Fig. 2. It was found that the properties of the recrystallized arc-melted columbium from all three heats showed very close agreement except at temperatures between about 500" and 800°C. A reason for this range of disagreement will be suggested in the discussion. The generally good agreement, however, attests to the ability of cold-working and subsequent recrystal-lization to erase the effects of the three different primary breakdown procedures and to produce nearly equivalent structures in the samples derived from the three different heats. wesse13 reported tensile data on columbium having interstitial impurity contents between those of the

Jan 1, 1962

By H. S. Chiang, D. F. Lu, S. S. Peng

INTRODUCTION The most important element in a successful lingual mining is a good roof control. The modern longwall mining employs hydraulic powered supports for roof control at the face area. The application of hydrau¬lic powered support requires the knowledge of over¬burden strata behavior for proper selection of sup¬port type and capacity. Failure to do so could lead so serious loss. There are several methods available for determining the required support capacity (1-3). While these methods are simple for application, they do not include the complicated roof behavior observed in longwall mining. As research progresses and operational experience accumulates (4,5), the concept about the designing and selection of powered support improves. The design of a longwall powered support consists of three major phases: 1. structural integrity and stability of the powered support, 2. external loadings induced by the movements of the overburden strata, and 3. interaction between the support, roof and floor. Phase 1 involves structural analysis (5) and full-sized testing (6) of the supports. Its validity is limited by the accuracy of the assumed external loading because of the uncertainty about the actual loading underground. The third phase includes the reaction of the support and the floor to the movements of the overburden strata and vice versa. Among the three phases, the second phase concer¬ning the external loading seems to be the least known because of the complicated behavior of the roof strata. There are many unresolved problems. For example, does the main roof break periodically and cause periodic roof weighting in the face area? If so, are there any rules governing its behavior? How does the roof load on the support canopy! Finally, how can one determine the required support capacity and select a proper type of support to meet a certain roof behavior? In order to answer those questions, underground instrumentation and observations were performed at 4 longwall panels in 3 separate mines for the past two years. This paper summarizes the current findings. PANEL LAYOUTS AND EQUIPMENT EMPLOYED The three mines selected are all located in West Virginia; two in northern and one in southern West Virginia. As shown in Table 1, seam conditions (i.e. seam, depth and thickness) and panel layouts are different among the three mines. The most significant difference in equipment is the face powered supports. Three mines used three different types of shield; 2-leg caliper, 2-leg lemniscate, and 4-leg lemniscate chock-shield. (Fig. 1) UNDERGROUND INSTRUMENTATION AND OBSERVATION PROGRAM Two events were instrumented in each observed longwall face: one was the hydraulic pressure (resistance) of the powered supports and the other was the canopy load distributions. In addition, the gob caving conditions were visually observed and recorded. Leg and Support Resistances One or two automatic Weksler Pressure Recorders were installed at the designated shield support,. In most cases, the daily charts were used to record the pressure variations in both the front or the rear legs (for the 4-leg shield), or in both the leg and the fore-pole ram (for the 2-leg shield). The recorded pressure w a s then converted to load or resistance by multiplying it by the cross-sectional area of the hydraulic leg or canopy ram piston. Fig. 2 shows the typical pressure-recorded charts for the 4-leg and 2-leg shields in a 23-24 hour period. The support resistance is the summation of the resistance in each of all the legs for that support. Generally, the resistance of the fore-pole ram will not be considered in determining the capacity of the support because of its rather small vertical compo¬nent force at the tip of the fore-pole. Canopy Load Distribution External load distribution on the canopy as exer¬ted by the roof was monitored. The measurements employed 12-14 pieces of pressure cells (6-inch square) that were uniformly arranged in two rows on the canopy. After support setting, the pressure changes in the cells were monitored at various stages of the mining (supporting) cycle while the support leg pressures were recorded continuously by the pressure recorders. Based on the calibration chara¬cteristics of each pressure cell as performed in the laboratory before and after each underground test, the cell pressures were converted to actual loadings. From these load measurements the canopy load distri¬butions and the relations between measured canopy loadings and support leg resistances were determined. Accordingly, the supporting efficiency of the shield support can be determined.

Jan 1, 1982

By W. A. Oates, J. A. Lambert, P. T. GaIIagher

Monte Carlo methods have been used to compute the arrangements of interstitial atoms dissolved in tetrahedral sites in bcc lattices. It is assumed that the presence of an interstitial atom "blocks " a certain number of neighboring sites and prevents their occupancy. Sites "blocked" by more than one filled site are allowed for. The computed values of. the mean occupation number (defined as the ratio of the total number of sites blocked to the number of solute atoms are used to calculate the configurational entropies of the solutions. These entropies are compared with those resulting from previous theoretical studies of this problem and also with available experin~ental data for the p Zr-H, Nb-H, V-H, and Ta-H systems. Evidence is also given that the "blocking" explanation of low limiting compositions in these systems, rather than this being due to initial limitations on the number of sites available, is probably correct. THE ideal partial configurational entropy of mixing of an interstitial solute in a metal is given by: where p is the number of interstitial sites per metal atom and Xi is the atomic fraction of the interstitial. For the bcc lattice. which we shall be concerned with in this paper, the interstitial positions are shown in Fig. 1. It can be seen that for the tetrahedral sites, p=6. whereas for the octahedral sites, p = 3. Different emphasis has been placed on the relative importance of energy and entropy effects in determining deviations from ideality in interstitial solid solutions. In some cases the same system, e.g., Fe-C, has been described by the contradictory regular and athermal solution models indicating that the enthalpy and entropy functions, derived from equilibrium data, are frequently not accu.rate enough to differentiate between these treatments. However, for certain metal-hydrogen solutions the equilibrium data is available over sufficiently wide ranges of temperature and composition to permit a reasonably accurate determination of the compositional variation of the heats and entropies. Hoch&apos; has attempted to interpret the results of interstitial solid solutions in terms of a regular solution model. In the case of the Ta-H system where 13 = 6, this model entails fitting the experimental relative partial entropies of solution, asH, to the equation: where ASgs is the relative partial excess entropy of solution of hydrogen. Hoch found that the results of Mallett and Koeh1 could be fitted to this equation with an approximately constant value of AF up to XH = 0.25. However, it is apparent from the solubility isotherms in this system which become asymptotic to the composition TaH that, since (Xh /6 - ~Xh ) becomes infinite only at TaH6, it is necessary that AS<&apos; tends to infinity at TaH. In other words, the low saturation composition of TaH, instead of the anticipated TaH,, eliminates the possibility of applying regular solution theory to such systems. Rather large negative excess configurational entropies must exist at higher hydrogen concentrations in order to explain the lower saturation values. To account for these low limiting compositions and excess entropies two distinctly different approaches have been followed. Rees and many others1-l2 have assumed that not all interstitial sites are crystallographically equivalent with respect to the interstitial addition; that is, in Eq. [I] p is less than the value anticipated from geometrical considerations. To describe, say, a bcc metal-hydrogen system with a limiting composition of MH by this approach one would consider that p = 1 in the first instance instead of p = 6.&apos;j3 In some cases, nonintegral values of B have been taken in order to improve the fit with the experimental data over limited ranges of composition. The other approach which has been used to explain the low saturation compositions is to assume that, although all sites are available for occupancy, strong repulsive interactions exist between the neighboring interstitial atoms, and hence occupancy of any site excludes or blocks a certain number of neighboring sites from being occupied. Earliest treatments of this concept considered the exclusion of an integral number, of nearest-neighbor sites from being occupied at all concentrations. In this case, the partial configurational entropy is given by: These early treatments failed to allow for the overlap of the blocked sites which will arise at all but the very lowest concentrations. More recently attempts have been made to calculate the effect of this decrease in the number of blocked sites on the configurational entropy. Using the quasichemical treatment of interstitial solid solutions as given by Lacher and assuming that an infinite repulsive interaction energy existed between the solute atoms. atom obtained an approximate configurational entropy applicable to the blocking with overlap case:

Jan 1, 1970