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By S. J. Hruska

Rate expressions for the formation of two-and three-dimensional nuclei on foreign substrates are developed, taking into account previously neglected contributions to the standard Gibbs free energy of formation of critical nuclei. The temperature dependence of critical super saturation data predicted using these expressions is in accord with data for cadmium on copper and sodium on CsCl. EXPERIMENTAL data on the heterogeneous nuclea-tion of metal crystals from the vapor phase1&apos;2 exhibit the temperature dependence predicted by a nucleation rate equation derived by Pound et al.3 In their treatment, the critical nuclei are visualized according to the Volmer4 model as cap-shaped (three-dimensional). Accordingly, it seems desirable to compare these data with a nucleation rate equation which is derived on the assumption of disk-shaped (two dimensional) nuclei. Further, Lothe and Pound5 have recently shown that the standard Gibbs free energy of formation of these critical nuclei contains a contribution which has heretofore been neglected. Thus it is necessary to re-examine these nucleation data using a rate equation which contains this contribution. The van&apos;t Hoff isotherm relates n(i), the concentration of nuclei of critical size i (i = number of atoms), to nil), the concentration of adsorbed single atoms: where standard Gibbs free energy of formation of critical nuclei given by is temperature insensitive and is the bulk free energy change/volume of transformed material], T = substrate temperature and k = Boltzmann&apos;s constant. Previously,3 was determined by considering only the contributions of bulk and surface free energies in transforming i atoms from the population nil) to a cluster of i atoms. It has been shown5 that this procedure does not take into account the free energy contribution arising from the multiplicity of sites, q, where the clusters can be situated. If this contribution, -kT In q/n(l),is added to iG3 [Note that this increases n(i) by a factor q/n(l).] Since the above does not affect the remaining terms in the rate expression of Pound et al., the details are referred to their paper. The resulting nucleation rate is If the experimental AGV and T values at some common value of are employed, a plot of vs T(ln C3/l + In p&apos;) should yield a straight line of slope k/B<p and intercept . The corresponding plots for / = 1 nucleus per sq cm sec and C3 = 1018 are shown in Figs. 1 and 2 for cadmium on copper1 and sodium on CsCl2 and the values of obtained therefrom are entered in Table I. It is apparent that the data yield reasonable straight lines with about the same scatter as found using the equation of Pound et al. When the configuration of minimum free energy for a nucleus is a circular monatomic layer, the standard free energy of formation is

Jan 1, 1963

By R. J. Walter, W. T. Chandler

The Ch-H phase diagram was determined for by-drogen concentrations up to ChHo.9 at temperatures below 400°P&apos;. The phase diagram includes a mis-cibility gap and a eutectoid transformation. A peri-tectoid transformation is postulated at the hydrogen-rich end of the diagram, Phase diagrams were determined for two levels oj purity, of the columbium. A single solid solution exists in the Cb-H system above 400°F. There has been considcrable disagreement among investigators concerning the system at temperatures below 400°F. Albrecht, Goode, and ~allett&apos; proposed a miscibility gap containing two bcc phases with the two lattice parameters converging at about 140°C (285-F), and Brauer and ~erman&apos; found a two-phase room-temperature region between 10 and 41 at. pct H. At sufficiently high hydrogen concentrations in the one-phase region, the hydrogen-rich phase was found to be face-centered orthorhombic. Wainwright, Cook, and Hopkills3 recently reported that the face centered orthorhombic hydride phase is derived from a unit cell which is slightly tetragonal with a small departure from 90 deg of the angle (y) opposite the r axis. The orthorhombic hydride phase was observed for hydrogen concentrations between 0.2 and 0.8 H/Cb atom ratio. Paxton and coworkers4 found that needlelike hydride plates formed in a hydrogen-charged columbium single crystal and suggested that this transformation possessed the characteristics of a diffusionless phase transformation. On the basis of room-temperature, X-ray diffraction data, komjathy&apos; suggested that an order-disorder or martensitic transformation occurs. In the present study, the Cb-H system was investigated to resolve the discrepancies found in the literature for this system. PROCEDURE The columbium specimens were prepared from two heats of wrought 1/2-in.-diameter electron-beam melted columbium rod and from two columbium powders of -80 mesh size of different impurity contents. The columbium bar stock was pur chased from Urah Chmg Corp.; the 99 and 99.5 pct purity colulnbium powders were obtained from Fansteel Metallurgical Corp. and Kern Chemical Co.. respectively. The chemical analyses of the columbium bar and powders are listed in Table I. Hydrogen charging was performed by exposing the columbium specimens to hydrogen at 1 atm pressure at various temperatures. After exposure the specimens were quenched to prevent the hydrogen pickup which would take place if cooled in hydrogen, or the hydrogen loss that would occur if cooled in an inert gas. Adequate hydrogen purity was achieved by passing high-purity tank hydrogen (maximum 5 ppm total impurities) through an Engelhard catalytic Deoxo unit, magnesium per chlorate desiccant, and finally through activated charcoal at the temperature of boiling nitrogen. Activated charcoal at -321°F has been reported6 to remove impurities from hydrogen to a nondetectable level. A schematic representation of the heat-treating apparatus is shown in Fig. 1. A metal-sheathed thermocouple embedded in the colun~bium specimen was used to control the temperature during heat treatment and to pull the specimen boat into

Jan 1, 1965

By L. E. Young

LOADING machines may be classified in several ways: (1) Machines which cut or break down and load .the coal; (2) machines which simply load the coal; (3) devices which load and transport the coal; (4) de-vices which elevate; (5) devices which transport the coal after it has been shoveled onto the device. There are many types of mechanical loading devices, Bull. 17, Coal Mining Investigations, under the auspices of Carnegie Institute&apos; of Technology, U. S. Bureau of Mines, and the Advisory Board, listing 31 exclusive. of -the large shovels used in thick coal seams. Mechanical loading of coal is not in its infancy; I think some of the early patents go back to 1890. One large coal company, properly called the early leader in this field of mechani-zation, has about 26 large machines at work. This company spent about thirty years in developing a ma-chine, and at the present time is loading approximately two million tons of coal a year in its mines. The chair-man directed a question at the previous speaker; inquir-ing if real progress was being made in mechanical load-ing. The experience of the company just referred to is in itself an adequate answer. A review of a list of mines using mechanical loading devices shows that there are 28 mines which we may say are 100 per cent mechanical. There are four more mines which have been 100 per cent mechanical, but which are idle at this time on account of labor condi-tions. There are at least 25 more at which the tonnage is more than 50 per cent mechanical. In speaking of a 100 per cent mine I do not mean that every pit car of coal is loaded by machine, because when complete, re-covery of the coal is attempted it is not practical to load all the coal at, the break line. In order to load the last 5 to 10 per cent of coal with a minimum of gob material and in order to keep the. working places along the break line timbered in a safe manner it is generally desirable to use a few hand loaders. At a certain mine operat-ing on the block system 90 percent of the coal is being loaded by what is properly a mechanical loading: device, and about 10 per cent -is being loaded by hand. This 10 percent is right off the break line, out of what might be called, the screen pillar. The mines referred to are scattered over the country, . in seven different&apos; States, and the equipment used is produced by ten different machinery companies. As to size, these mines vary from small mines of 500 tons mining capacity-up. In one instance a company with one loading machine is producing an, average of 450 tons per day. One of the large mines that is idle pro-duced at the. rate of 4300 tons per day, of which 97 per cent was actually loaded by machinery.

Jan 8, 1928

By Ben Gumpertz

The important factors in any study of the screening of sand with a gravel envelope, as applied to use in oil wells, are: (I) sand size and shape, (z) gravel size and shape, (3) ratio of gravel size to sand size, (4) flow velocity, (5) viscosity of the fluid. Perhaps the first extensive investigation of the function of gravel in screening sand was performed by Coberly and Wagner,&apos; from which the following conclusion was drawn: "The diameter of the largest grains in a single classified sand suitable for gravel packing is approximately 13 times the grain size at the ten-percentile analysis of the formation sample." ?;his applies to sands classified by Tyler screens and is for gravel grains of the maximum size that could be used to form a stable bridge. Field practice has shown that the screening effect of a given gravel for a given sand apparently varies with the flow velocity." Also, it has been assumed by some operators that the thickness of the walls of the gravel envelope surrounding the well has little effect upon the screening process. It is thought by others that a narrow envelope of gravel might form an ineffective screen. Thus the purposes of this work are: 1. To investigate the effect of gravel-sand size ratio upon screening action under the condition of varying flow velocities. 2. To investigate the effect upon screening action of varying the thickness of the gravel screen. 3. To investigate sand migration in the gravel screen and the effect of flow velocity and gravel size upon sand migration. Description of Apparatus In an attempt to reproduce field conditions for the purposes of this investigation, a flow tube was constructed, according to the manner of Urenj3 to represent a radial drainage segment of an oil sand. To arrive at the dimensions of the flow tube, a radial drainage segment of rectangular cross section was assumed to define an area of z sq. in. on the face of a well 6 in. in diameter. From this the dimensions of the segment were calculated out to a distance of 5 ft. from the face of the well. By computing cross-sectional areas at a number of sections along the rectangular segment and transforming these areas into the circular form, a drainage cone was obtained having everywhere the same cross-sectional area as the drainage element of rectangular cross section. To construct the apparatus, two sections of pipe of 7%-in. inside diameter, one 13 in. and the other 4 ft. long, were joined by a bolted flange. A mandrel having the dimensions of the drainage cone was centered in the pipe and a neat cement mixture was cast around it. A protective gasket was placed between the two sections of pipe so that the cement body could be separated at that point. When the mandrel was withdrawn a drainage cone was obtained (Fig. I).

Jan 1, 1941

By Ben Gumpertz

The important factors in any study of the screening of sand with a gravel envelope, as applied to use in oil wells, are: (I) sand size and shape, (z) gravel size and shape, (3) ratio of gravel size to sand size, (4) flow velocity, (5) viscosity of the fluid. Perhaps the first extensive investigation of the function of gravel in screening sand was performed by Coberly and Wagner,&apos; from which the following conclusion was drawn: "The diameter of the largest grains in a single classified sand suitable for gravel packing is approximately 13 times the grain size at the ten-percentile analysis of the formation sample." ?;his applies to sands classified by Tyler screens and is for gravel grains of the maximum size that could be used to form a stable bridge. Field practice has shown that the screening effect of a given gravel for a given sand apparently varies with the flow velocity." Also, it has been assumed by some operators that the thickness of the walls of the gravel envelope surrounding the well has little effect upon the screening process. It is thought by others that a narrow envelope of gravel might form an ineffective screen. Thus the purposes of this work are: 1. To investigate the effect of gravel-sand size ratio upon screening action under the condition of varying flow velocities. 2. To investigate the effect upon screening action of varying the thickness of the gravel screen. 3. To investigate sand migration in the gravel screen and the effect of flow velocity and gravel size upon sand migration. Description of Apparatus In an attempt to reproduce field conditions for the purposes of this investigation, a flow tube was constructed, according to the manner of Urenj3 to represent a radial drainage segment of an oil sand. To arrive at the dimensions of the flow tube, a radial drainage segment of rectangular cross section was assumed to define an area of z sq. in. on the face of a well 6 in. in diameter. From this the dimensions of the segment were calculated out to a distance of 5 ft. from the face of the well. By computing cross-sectional areas at a number of sections along the rectangular segment and transforming these areas into the circular form, a drainage cone was obtained having everywhere the same cross-sectional area as the drainage element of rectangular cross section. To construct the apparatus, two sections of pipe of 7%-in. inside diameter, one 13 in. and the other 4 ft. long, were joined by a bolted flange. A mandrel having the dimensions of the drainage cone was centered in the pipe and a neat cement mixture was cast around it. A protective gasket was placed between the two sections of pipe so that the cement body could be separated at that point. When the mandrel was withdrawn a drainage cone was obtained (Fig. I).

Jan 1, 1941

By D. R. Pratt, R. W. Hanks

The method of Caldwell and Babbitt for detennining Bingham plastic rheological constants from engineering pipe flow data has been erroneously used in many previous applications. A reanalysis of extensive pipe flow data from the literature is performed. Critical Reynolds numbers corresponding to the laminar-turbulent transition calculated from these data are found to agree with theoretically calculated values for the entire flow range studied. Similar agreement is found for the authors&apos; own data&apos; for flow of 10 slurries between parallel plates. The Bingham plastic model is shown to be a reliable representation of the flow of non-Newtonian slurries provided it is properly applied. If the Hedstrom number He = pD2 t0/?2 > 104, then the linear approximation method of Caldwell and Babbitt is invalid for pipe flow data obtained in systems of ordinary engineering interest, and the complete nonlinear form of the pipe flow Bingham plastic equation must be used in determining rheological parameters. INTRODUCTION Many materials of engineering interest must be handled and transported as slurries or suspensions of insoluble particulate matter in a Newtonian liquid. These suspensions frequently exhibit non-Newtonian rheological behavior which is reasonably well described by the simple Bingham plastic rheological equation1 Using this particular equation to describe the laminar flow characteristics of slurries was discussed at length by Caldwell and Babbitt2-4 who considered the flow of various clay slurries and sewage sludges. The model has since been used by many others.5-7 More recently the problem of predicting the laminar turbulent transition Reynolds number for Bingham plastic fluids has been treated8 for the case of flow in pipes. This paper points out errors which have existed in the analysis of Bingham plastic flow since the work of Caldwell and Babbitt2-4 and presents a reanalysis of the laminar turbulent transition calculatiod for Bingham plastic flow in pipes. In addition, new data obtained for flow of Bingham plastic slurries between parallel plates, both in laminar flow and in the laminar turbulent transition region, will be presented and compared with the theoretical analysis of laminar turbulent transition for flow between parallel plates. THEORETICAL ANALYSIS PIPE FLOW The mathematical analysisl-4 of laminar flow of a Bingham plastic fluid leads to the following equation. where q = <v>/R is a pseudoshear rate, rw is the wall shear stress Eo = r0/rw, r0 is the yield stress and 1 is the coefficient of rigidity or plastic viscosity from Eq. 1. Caldwell and Babbitt2-4 recognized that the quartic term in Eq. 2 was small compared to the other terms whenever 5, « 1, and that for large values of 7, a plot of Eq. 2 becomes linear. The slope of such a plot with rw as ordinate is 4? and the intercept is (4/3) ro. This approximation is illustrated schematically in Fig. 1. The shaded region between the true curve and the straight-line approximation near the origin represents the contribution of the quartic term. In principle, therefore,

By H. W. Hitzrot, R. H. Limons, L. V. Fegan

The testing of a new method for measuring pellet-bed temperatures in the traveling-grate or shaft furnace is presented in this paper. This method, using silver-palladium alloy wires as indicators, overcomes disadvantages existing in the methods based on the use of thermocouples which are costly and time-consuming. The authors have developed and tested a new method for measuring pellet-bed temperatures in the traveling-grate or shaft turnace through the use of silver-palladium alloy wires as indicators. This method overcomes the disadvantages of existing methods, which, based on the use of thermocouples, are generally costly and time-consuming. For example, in the case of the traveling-grate furnace, the installation of an instrumented pellet, together with its attached thermocouples, requires stopping the furnace, with resulting loss of production time. As for temperature measurement in the shaft furnace by the existing method, the movement of the shuttle-car feeder seriously interferes with both the actual insertion and the resulting distribution of continuously fed thermocouples. The authors have overcome these difficulties by using, as temperature indicators, a range of silver-palladium alloy wires that can be easily recovered, after firing at any desired location in a pellet furnace. Silver-palladium wires having specific melting points from 2000°F to 2500°F are enclosed in ceramic capsules. Each capsule is placed in a ni-chrome wire basket filled with a sample of green pellets, the baskets being the means for recovering the capsule after firing. After the encapsulated wires have been exposed to the firing cycle, the alloy wires are examined to determine the maximum temperatures attained by the pellet sample. This method gives accurate, rapid determinations of maximum temperatures attained during pellet induration in either the traveling-grate or shaft furnace The new method has the following advantages over existing methods: 1) it is less expensive; 2) no furnace downtime is required; 3) the testing units can, be made in quantity in advance; 4) measurements can be made in rapid succession at all desired locations; 5) measurements of maximum firing temperatures are more accurate; 6) on the basis of points 4 and 5, the new method gives a more reliable picture of the correlation of pellet quality, petrographic textures and maximum temperatures, thus providing a more effective quality-control tool. A disadvantage of the method is, of course, that the measurements are not continuous and only maximum temperatures are determined. TEST PROGRAM Preparation of Materials: CALIBRATION OF ALLOYS - In the following discussion the term "bead point" (see Fig. 1) refers to the temperature at which each alloy begins to melt and form a bead. Fig. 2 gives the bead point curve for silver-palladium alloys. Before the alloys are used in plant tests, the bead point of each alloy should be determined in the laboratory to verify the alloy compositions. Once a given alloy has been calibrated, it can be

Jan 1, 1965

By Cyril Stanley Smith

ON the 6th of February 1684, Dr. Martin Lister mentioned at a meeting of the Royal Society1 that "brass is magnetical," and promised to give an account of that assertion at some other time. He repeated his promise but never fulfilled it, and it was left for William Arderon2 to show, in 1958, that brass could be made magnetic by hammering and that it would retain polarity after magnetizing. Twenty-seven years later Cavallo3,4 examined the matter in great detail. Working with cast calamine brass, he showed that it could be made magnetic by hammering and nonmagnetic by subsequent annealing at a red heat. He found that annealing at a very high temperature caused the samples to lose their magnetic quality permanently, even after subsequent cold-working, but that remelting and cold-working restored it. He encountered some samples of brass that could not be rendered magnetic by any treatment. Experiments in which these were remelted with iron additions gave negative results, and Cavallo concluded that iron impurity was not the cause of the magnetism. He worked with 50-grain (3-gram) samples melted under the blowpipe, hence cooled very quickly. Bennet5 made whole crucible charges from copper and zinc, and found the resulting brass ingots to be magnetic only when iron had been added and then only after cold-working. All these observations applied to material in the cast condition, in which coring would produce a continuous spectrum of composition and cooling would result in varying degrees of precipitation. This knowledge of the subject seems to have been forgotten in the nineteenth century. The older brass was made by the calamine process and frequently contained iron in amounts of 0.5 per cent or more, absorbed from the impure ore with which the copper and charcoal were heated in making the brass. When metallic zinc became available in commercial quantities, calamine brass gradually disappeared, and with it the knowledge of its curious magnetic properties. Only when sensitive apparatus replaced the compass needle of the earlier investigators could the effects be detected in relatively pure metal. The effect of cold-working in inducing ferromagnetism was rediscovered by Bitters in 1930 in a sample of impure copper, and this was confirmed by Lowance and Constant,9 Honda and Shimizu, 10,11 and others. In the same year, Tammann and Oelsen12 showed that copper-rich copper-iron alloys after certain heat-treatments could be rendered ferromagnetic or made more strongly ferromagnetic by cold-rolling. Kussman and Seeman13 showed that the change of susceptibility of relatively pure copper on cold-working was associated with the iron content, and concluded that actual precipitation of iron was caused by cold-working, which is a satisfactory theory until one considers the improbably high rate of diffusion that this would involve. When studying precipitation phenomena in

Jan 1, 1941

By Emma Smith, R. W. Guard

INVESTIGATION of the nickel-rich end of the Ni-Zr system has been prompted by an interest in the effect of small amounts of zirconium in high temperature alloys. Hansenl presents a hypothetical diagram based on the work of Allibone and Sykes,2 who investigated the system up to 44 atomic pct (55 wt pct) Zr by metallographic means. Since the alloys they used were melted in Alundum crucibles they were probably contaminated with appreciable amounts of aluminum. They found two compounds which they called Ni3Zr and Ni4Zr. Hayes, Roberson, and Paasche3 identified a compound NiZr (50 atomic pct Zr) with a melting point of 1470°C. Such a high melting compound is not compatible with the observation of Allibone and Sykes2 hat a eutectic is formed near 50 atomic pct. The alloys containing up to 60 atomic pct Zr were melted in an inert atmosphere in a noncon-sumable electrode arc furnace. Analysis of most of the alloys indicated negligible loss of zirconium. The alloys were examined in the as-cast condition and also after annealing for 6 hr at 1175°C (or 1000°C for the alloys between 25 atomic pct and 45 atomic pct). Metallographic specimens were etched using mixtures of HF-HNO3-H2O or acetic acid- HN0,-H,O. The specimens for the solidus determinations were wrapped in molybdenum foil and sealed in evacuated quartz tubes. Specimens to be heated above 1300°C were enclosed in zirconia tubes inside the quartz to prevent reaction with molybdenum. The solidus determinations were carried out by heating the specimens at various temperatures for a few minutes and then examining the interior structure metallographically to determine at what temperature melting began. The 150 mesh powders for X-ray analysis were annealed in an evacuated quartz tube for 2 hr at 540 °C to remove cold work. Alloys with 22.5 atomic pct Zr and 44.4 atomic pct Zr required annealing at 700 °C for complete recovery. The grains of both of these alloys were soft and rather ductile. Both Debye-Scherrer film patterns and spectrometer traces were made for each alloy using filtered copper radiation. Results and Discussion The presence of a substantial amount of second phase in an alloy with 1.1 atomic pct Zr indicated that the solid solubility of zirconium in nickel is somewhat less than 1 atomic pct. The a0 value for the face-centered-cubic matrix in the same alloy was equal to that of pure nickel, so that the solubility must be very small. This observation is as expected from the large atom size difference. Annealed specimens of alloys with 15.0, 16.7, 22.5, 28.6, 44.4, and 59.4 atomic pct Zr showed. micro-structures that were essentially single phase. When

Jan 1, 1958

By S. C. Sircar, B. K. Dhindaw

KINETICS and mechanism of sulfation reactions have been studied extensively. Qualitative and quantitative data are reported for the kinetics and mechanism of sulfation reaction of copper oxide pellets;&apos;&apos;2 yet it remains a controversial Subject. The mechanism and kinetics of the sulfation of zinc oxide powder (B.D.H. analar quality) were studied by gravimetric technique. A spring of high-carbon steel wire with accuracy well within 0.2 mg was used for measuring weight change. The sample was taken in a Pyrex glass bucket, hanging freely inside a Pyrex glass tube reactor, with a gold wire attached to the spring, the reactor being surrounded by a movable furnace (double wound type) with a temperature control within *5"C. Flow of oxygen, 60 cu cm per min, and sulfur dioxide, 45 cu cm per min, were measured through calibrated flowmeters and the mixture dried over PZ05 before entering the reactor. The experimental results are presented in Figs. 1 and 2. The plot of weight change of zinc oxide, giving the amount of zinc sulfate formed, was found to be linear over the temperature range of 500" to 700° C and up to a conversion of approximately 60 pct, as beyond it they divert from linearity.&apos; The rate of sulfation was found to be affected by total flow rate of gases at a fixed ratio of SO2/O2, up to 60 cu cm per min, and was found to be linearly dependent on quantity of total powdered sample taken. The plot of rate of sulfation of zinc oxide, 70 mg, with varying amounts of vanadium pentoxide, at a constant ratio of gases as mentioned above, and at a constant temperature of 625"C, was also found to be linear as seen in Fig. 2. Extrapolation to zero V2O5 addition gives the same rate of sulfation, as in case of pure zinc oxide, 70 mg. Vz05 was prepared by heating ammonium vanadate at 600°C for 15 min in a muffle furnace. The available literature points out that the theory of sulfation that has received the maximum support postulates the following mechanism for sulfation of ZnS: 2ZnS + 30, = 2Zn0 + 2SOZ; the ZnO formed acts as a catalyst for the reaction, 2 S02 + O2 = 2S03. This SO3 reacts with ZnO to give zinc sulfate. It is suggested here that the above widely supported mechanism is operative in the sulfation reaction and that the rate-controlling step in the sulfation reaction of ZnO is the formation of SO3 from SO, and 0,. The authors are carrying on further work in this line, and the details will be published later. The authors wish to acknowledge the facilities provided and the help extended by Prof. P. R. Dhar, Head, Department of Metallurgical Engineering, and the permission granted to publish this note by the Director, I. I. T., Kharagpur.

Jan 1, 1969

By J. W. Fredrickson

VERY little information is available in the literature concerning the solubility of magnesium in titanium. Aust and Pidgeon&apos; report the solubility of titanium in magnesium to be 0.0025 pct at 650°C and 0.015 pct at 850°C. X-ray diffraction studies failed to detect any evidence of solid solubility. Based on the fact that the addition of titanium to magnesium increases the c/a ratio of magnesium, Busk&apos; suggested that the Mg-Ti system, like the Mg-Zr, is a peritectic. Eisenreich- eported the solubility of titanium in magnesium to be 0.003 pct at 655°C and 0.064 pct at 760°C. Removal of hydrogen from the melt increased the solubility of titanium to 0.115 pct at 800°C. Eisenreich proposes a peritectic-type diagram for the high magnesium side of the system. Recent work&apos; with Ti-Mg diffusion couples indicate that the solid solubility of titanium in magnesium is extremely small and that there is limited solid solubility of magnesium in titanium. Experimental work on the Ti-Mg system is complicated by the fact that the boiling point of magnesium is considerably below the melting point of titanium. Consequently, the usual alloying methods are impractical. Alloying was accomplished in this investigation by sheath-rolling compressed compacts." The alloys were made from titanium sponge and high purity magnesium. Chemical analysis of the sponge showed 0.04 pct Mg, <0.005 pct Al, <0.001 pct Cu, 0.05 pct Fe, 0.022 pct Mn, <0.0025 pct Ni, 0.007 pct Si, <0.005 pct V, and <0.01 pct Zn. All heat treating was conducted in a protective atmosphere by encapsulating the specimens in fused silica ampules under a partial pressure of helium. Equilibrium was achieved by holding the specimens at temperature for periods of 24 to 120 hr. The alloys were hot rolled, cold rolled, and annealed prior to solution heat treatment. Fig. 1 shows the constitutional diagram obtained for the Ti-Mg system up to 1.5 pct Mg. Oxygen was known to be present in the alloys; therefore, it is necessary to consider the alloys as ternary rather than binary and the diagram should be viewed as a plot of a section through the Ti-Mg-0 system. Other investigatorso have shown that the addition of oxy- gen to titanium stabilizes the a phase. The data presented in Fig. 1 indicate that the addition of magnesium to titanium tends to stabilize the p phase. Armour Research Foundation7 has shown that the addition of magnesium to zirconium lowers the a transus and is classified as a p stabilizer in that system. Magnesium is soluble in solid titanium to the extent of at least 1.5 pct in both the a and /3 phases. No intermetallic compounds or magnesium-rich phases were observed either by light microscopy or X-ray diffraction. However, this does not negate the possibility that such phases exist at higher alloy concentrations.

Jan 1, 1956

By H. C. Chao, Y. E. Smith, L. H. Van Vlack

ThE phase relationships for the MnO-MnS system have been investigated only in the eutectic region. wentrupl reported a eutectic at 1280°C (2345°F) with approximately 50 wt pct of each component, as based on the earlier work of Andrew, Maddocks, and Fowler.2 More recently silverman3 corrected these figures to 2275° ±10°F (1246°C) with 63 wt pct MnS and 37 pct MnO. Neither Wentrup nor Silverman investigated the solid-solution limits in this system. However, Wentrup did suggest with his phase diagram sketch that the maximum solubility of MnS in MnO is 10 wt pct, and the solubility of MnO in MnS is nearer 20 wt pct, Fig. 1. These figures have been utilized in subsequent publications without further verification.4 There had been evidence found in this laboratory that the above solid-solution figures were high. An investigation was therefore conducted using the following procedure. Samples containing MnO and MnS were contained in platinum foil, heated just above the eutectic temperature in a purified nitrogen at- mosphere, and quenched into distilled water. The MnO had been prepared by calcining reagent grade MnCO3 in nitrogen at 1400°C. Only MnO was detected in subsequent X-ray diffraction analyses. The MnS had been prepared by sulfur deoxidation of reagent grade MnSO4 according to the reaction: MnSO4 + S2 ? MnS + 2SO2 The details of the sulfide preparation procedure, which utilized atmospheric sulfur pressures at 950°C, are discussed elsewhere.5 The sulfur content of the sulfide was determined to be 36.8 * 0.2 pct, which matches the stoichiometric value of 36.9 pct. No evidence of either MnO or MnSO4 was detected microscopically or by X-ray diffraction. The single-phase combinations of MnO and MnS at the eutectic temperature indicate the limit of solid solution as shown in Fig. 2(a) and (c), and the revised phase diagram is shown in Fig. 2(d). The melting temperature for MnO is that provided by Glasser.6 The eutectic temperature of 1232° ± 5°C and eutectic composition of 64 wt pct MnS are in close agreement with Silverman&apos;s correction of Wentrup&apos;s work. The maximum solubility of MnO in MnS was determined to be 1.7 ± 0.2 wt pct. The maximum solubility of MnS in MnO was determined to be 1.8 ± 0.2 wt pct. These figures represent the lower limit for the presence of liquid at 1260°C and are significantly lower than the earlier estimated solid-solution figures. The authors wish to acknowledge the support of U.S. Steel&apos;s Edgar C. Bain Laboratory for Fundamental Research. The comments and critical suggestions of Drs. A. S. Keh, R. Rickett, and R. B. Snow are appreciated.

Jan 1, 1963

By B. D. Cullity

A distribution of residual stress after plastic elongation is proposed, in which the bulk of the material is strained in compression and a very small portion in tension, This distribution is shown to account both for the X-ray observations and for the effect of plastic straining on magnetic losses in silicon steel. The regions left in compression are tentatively identified with the interiors of the sub-grains revealed by the electron microscope. THIS paper is concerned with the general problem of the nature of the residual stress which is produced in metals by plastic elongation. A particular stress distribution will be suggested which accounts for the main X-ray diffraction observations which have been made. It will also be shown that certain magnetic measurements made on silicon steel can be understood in terms of this stress distribution. X-RAY OBSERVATIONS Uniform straining of a crystal lattice (macro-strain) causes a diffracted X-ray beam to shift its position, and nonuniform straining (microstrain) causes line broadening. If a bar of metal is plastically elongated in the longitudinal x direction and then unloaded, diffracted X-ray lines are observed to be both shifted and broadened.&apos;-= Although the observed line shift indicates the presence of macro-strain, experiments have shown that no macrostrain, in the usual engineering sense of the term, exists.5"7 For example, removal of a layer from one surface of a stretched and unloaded bar does not produce curvature in the remainder of the bar 5&apos;7 Fig. 1 shows the variation of lattice strain in the x direction, as determined from X-ray line shifts, with the applied stress in the same direction. The curve ABC is the normal stress-strain curve of the material, AB being the elastic portion and BC the plastic. In the elastic region AB, the strain measured by X-rays, called the lattice strain, and the strain measured mechanically are both proportional to the applied stress, and both return to zero when the applied stress is removed. Above the elastic limit the lattice strain would be expected to continue to increase along the line BD. Actually, it increases less rapidly with respect to stress, or even decreases, as shown by BE. If the applied stress is then decreased, the lattice strain decreases along EF, which is parallel to AB. As a result, there is a compressive residual lattice strain FA after unloading. STRESS DISTRIBUTION. Since a stretched and unloaded bar does not contain macrostress, it follows that the observed line shift must be due to a special distribution of mi-crostress. Such a distribution is shown in Fig. 2, which shows the variation of the stress u, across a stretched and unloaded bar. The material is assumed to consist of two kinds of regions: regions C, stressed more or less uniformly in compression, comprising the bulk of the volume of the material and responsible for the observed diffrac-

Jan 1, 1963

By E. W. Dewing

The solubility of A14C3 in cryolite melts has been determined by holding the melt with aluminum in a graphite crucible for 4 hr at temperature, quenching the crucible in water, and analyzing the frozen salt by CH4 evolution. The solubility is given by log(wt % Al4C3) = 1.298 -1.l74 (wt ratio NaF/AlF3) independent of temperature in the range 985" to 1080°C. Additions ofA1203, .NaCl, CaF2, or LiF up to 10 wt pct do not affect the solubility, provided that LiF and CaF2 are replaced by equivalent NaFin calculating the ratio. The variation with ratio can be accounted for quantitatively on the hypothesis that the Mechanism of solution is Al4C3 + 2AIF3 = 3Al2CF2 since the solubility varies as (aAIF3) 2/3; Mechanisms involving C", C2- , AlC- , A12C2+, and Al2CF+are re-jected. At ratios above 1.5 truces of c;- are also present. It was noticed some years ago in this laboratory that carbon specimens made cathodic in a cryolite bath decrease in diameter over a period of time.&apos; It was also found that cryolite which had been melted with aluminum in a graphite crucible was sometimes yellow, and that A14C3 could be seen intimately embedded in the cryolite crystals. CH, could be recovered by acid attack. There was thus reason to believe that A14C3 had a genuine solubility in molten cryolite, and the object of this work was to measure it. EXPERIMENTAL AND RESULTS A graphite crucible, 2 in. ID and 2.5 in. deep with a close-fitting lid, contained about 150 g of cryolite (plus additives) and about 20 g of 99.99 pct pure Al. It was placed in a vertical Inconel furnace tube, covered with refractory brick to provide thermal insulation, and the top of the tube was roughly sealed with disks of asbestos paper. An alumina tube led argon down to the level of the top of the crucible to expel air, and an alumina sheath with a Pt-10 pct Rh ther-mocouple inside was positioned between the crucible and the wall of the Inconel tube. The tube was heated in an electrical resistance furnace for the desired length of time; the refractory bricks were then removed, and the crucible was lifted out with tongs and quenched in water. After such a crucible was broken open it could be seen that its inner surface was yellow owing to the presence of A1,C3, and sometimes needle-like crystals could be observed (at X75 magnification) growing out into the nielt. It was concluded that Al,C, had been present as a separate phase when the crucible was at tenlperature and that the melt had been saturated: in

Jan 1, 1970

By J. P. Smith

DURING the winter of 1946 to 1947 potash operations in Germany, France and Spain were visited by the author. The U. S. Department of Commerce, through its Field Intelligence Agency Technical, sponsored the inspection of German properties by representatives of the American Potash Industry. Vast deposits of potash salts occur in the above-mentioned countries, and the production and marketing of these salts are important in their respective economies. Germany An area of some ten thousand square miles of north central Germany is underlain by lenses of potash salts interbedded with greater thicknesses of sodium chloride or common salt. These salt measures are relict deposits from the evaporation of an arm of the Zechstein (Permian) Sea which formerly covered northern Europe. During the peak year of 1940, Germany produced salts containing 1,860,000 tons of K,O and, next to coal, potash is its most important mineral raw material. The German deposits are found in the synclinal areas flanking the Flechtingen, Hartz Mountain and Thuringian uplifts, and, to the north they lie beneath the plains of Hannover. The regional dip of the salt measures is to the north, hence, lenses of potash found at depths of 500 to 1000 m* in the Two general depositional provinces of potash concentrations are recognized: (1) the main basin, and (2) the subsidiary basin. The main basin embraces the producing districts of Stassfurt, Sud Hartz, Halle, and Hannover-Braunschweig. From J. P. SMITH, Member AIME, is Clzief Geologist, U. S. Potash Co., Carlsbad, New Mexico. New York Meeting, February 1948. TP 2621 H. Discussion of this paper (2 copies) may be sent to Transactions AIME before Feb. 28, 1950. Manuscript received May 26, 1948. 40 to 45 pct of the German production comes from this basin. The Werra-Fulda district, producer of 50 pct or more of the German potash, lies in the subsidiary basin. Salt Stratigraphy: Five commercial potash zones or beds are recognized. The three beds present in the main basin are: The Stassfurt bed that occurs near the top of the older salt, and the Ronnenberg and Riedel beds in the younger salt occurring 200 to 300 m, respectively, above the Stassfurt bed. The Stassfurt bed is found over the entire main basin, while the Ronnenberg and Riedel are restricted to the Hannover area. Two potash beds occur in the Werra basin. These are the Thuringian, or lower bed and the Hessen or upper potash bed that occurs 60 m above. These beds lie 210 and 150 m, respectively, below the position of the Stassfurt bed, and are restricted to the Werra basin. The upper bed is 2.5 to 11.5 m in thickness, and the principal ores are hartsalz with varying thicknesses of carnallite. The lower bed averages 3 m in thickness, and contains hartsalz. The upper bed is presently being mined, and the

Jan 1, 1951

By E. A. Nesbitt

The important permanent-magnet alloys 15 years ago contained carbon and depended upon it for their permanent-magnet properties. In recent years great advances have been made in a number of new alloys substantially free of carbon. These include Remalloy,&apos; an alloy of iron, cobalt, and molybdenum, the various iron-nickel-aluminum alloys of the Mishima2 type, and the more recent Alnico V3 in which the best properties are developed by heat-treating in a magnetic field. The Mishima and the Alnico types of alloys are very brittle and after casting must be ground to size. This article describes a permanent-magnet material4 that can be machined as cast, and when handled with some care can be rolled to thin sheet and drawn to fine wire. Optimum magnetic properties are developed by a simple heat-treatment, and at this time the ductility of the alloy disappears. If the cast alloy is heat-treated without cold-working the mag netic energy product is about 1.0 X 106. This material is called Vicalloy I (pronounced vicalloy, V for vanadium, I for iron, and C for cobalt). When the alloy is first hot-worked and then considerably reduced in area by cold-swaging, drawing or grooved rolling, it is found that after heat-treatment the magnetic energy product measured in the direction of previous extension can be increased to 2.0 to 3.5 X 106. These higher values have been obtained only after reductions in area of 75 to 95 per cent, and since the material hardens considerably during working, the reduction ordinarily can be accomplished only in fine wires, although larger sizes can be reduced by the use of powerful machinery. When the material has been cold-worked in such a manner as to improve its energy product substantially, it is called Vicalloy 11. Commercial use of Vicalloy has been made in the recording of speech. Tape 0.002 by 0.050 in. has been found superior in quality to all others tried, and is now used in the Western Electric Mirrorphone 5 In a variety of forms Vicalloy I or I1 is useful in many laboratory instruments, and in experiments in which the sizes and shapes required cannot be obtained with the other more brittle permanent-magnet materials. In 1936, during a study of other age-hardening magnetic systems, it occurred to the author that some of the iron-cobalt-vanadium alloys might be suitable for permanent magnets. The proportions of iron, cobalt, and vanadium were varied and a range of alloys of particular interest was found, as shown by the indicated area in Fig. I. The limits of this range of composition are 30 to 52 per cent iron, 36 to 62 per cent cobalt, and 4 to 16 per cent vanadium. The compositions indicated by points outside this area were also tested. Preparation and Properties OF Vicalloy I The alloys were usually cast in graphite molds into bars 3/4 in. in diameter and

Jan 1, 1946

By J. P. Smith

DURING the winter of 1946 to 1947 potash operations in Germany, France and Spain were visited by the author. The U. S. Department of Commerce, through its Field Intelligence Agency Technical, sponsored the inspection of German properties by representatives of the American Potash Industry. Vast deposits of potash salts occur in the above-mentioned countries, and the production and marketing of these salts are important in their respective economies. Germany An area of some ten thousand square miles of north central Germany is underlain by lenses of potash salts interbedded with greater thicknesses of sodium chloride or common salt. These salt measures are relict deposits from the evaporation of an arm of the Zechstein (Permian) Sea which formerly covered northern Europe. During the peak year of 1940, Germany produced salts containing 1,860,000 tons of K,O and, next to coal, potash is its most important mineral raw material. The German deposits are found in the synclinal areas flanking the Flechtingen, Hartz Mountain and Thuringian uplifts, and, to the north they lie beneath the plains of Hannover. The regional dip of the salt measures is to the north, hence, lenses of potash found at depths of 500 to 1000 m* in the Two general depositional provinces of potash concentrations are recognized: (1) the main basin, and (2) the subsidiary basin. The main basin embraces the producing districts of Stassfurt, Sud Hartz, Halle, and Hannover-Braunschweig. From J. P. SMITH, Member AIME, is Clzief Geologist, U. S. Potash Co., Carlsbad, New Mexico. New York Meeting, February 1948. TP 2621 H. Discussion of this paper (2 copies) may be sent to Transactions AIME before Feb. 28, 1950. Manuscript received May 26, 1948. 40 to 45 pct of the German production comes from this basin. The Werra-Fulda district, producer of 50 pct or more of the German potash, lies in the subsidiary basin. Salt Stratigraphy: Five commercial potash zones or beds are recognized. The three beds present in the main basin are: The Stassfurt bed that occurs near the top of the older salt, and the Ronnenberg and Riedel beds in the younger salt occurring 200 to 300 m, respectively, above the Stassfurt bed. The Stassfurt bed is found over the entire main basin, while the Ronnenberg and Riedel are restricted to the Hannover area. Two potash beds occur in the Werra basin. These are the Thuringian, or lower bed and the Hessen or upper potash bed that occurs 60 m above. These beds lie 210 and 150 m, respectively, below the position of the Stassfurt bed, and are restricted to the Werra basin. The upper bed is 2.5 to 11.5 m in thickness, and the principal ores are hartsalz with varying thicknesses of carnallite. The lower bed averages 3 m in thickness, and contains hartsalz. The upper bed is presently being mined, and the

Jan 1, 1951

By D. A. Dukelow, G. Derge

THE Fe0-Mn0-Si0, system has many properties of fundamental interest besides its occurrence in steel-making. The system is the simplest ternary complication of the FeO-SiO, binary whose electrochemical properties have been explored. Therefore, knowledge of the conformance of Fe0-MnO-SiO, melts to Faraday&apos;s laws, as investigated by current efficiency measurements, would be of particular value in interpreting the observed variations of electrical conductivity, while at the same time furthering understanding of this type of molten oxides. Pertinent to the present study are conductivity data of FeO-SiO, and Fe0-Mn0-SiO2, and current efficiency data of FeO-SiO,. Concerning conductivity measurements, Inouye, Tomlinson, and chipman&apos; studied the specific conductivity, a, of molten wüstite as a function of temperature and oxide addition. Liquid FeO in equilibrium with an iron crucible was found to have a o whose magnitude and positive temperature coefficient were undeniably semiconductor in nature (o1400°C = 269 ohm-1cm-&apos;). Additions at 1400°C of 5 mole pct MnO decreased o to 227 while a similar addition of SiO2, dropped o to 125. Additional SiO2 produced an exponential decline of o. It was reasoned that because wüstite is known to be oxygen excess and since there is no pronounced change in oFeO upon melting, that UFeO(L)is p-type semiconduction. Björling2 gives o data for the ternary FeO-MnO-SiO, using fayalite, 2 FeO-SiO,, as the base substance. Upon addition of tephroite, 2 MnO-SiO, he noted a small decrease in o. Taking his data for 1400°C with one-half of the fayalite replaced by tephroite, o shows a decrease of some 40 pct relative to o for fayalite, i.e., 5 ohm-&apos; cm-&apos; to 3. In line with this observation, Mori and Matsushita3 reported that substituting MnO for FeO in the silicate de- creased o slightly except at high SiO, contents where the decrease was somewhat larger. Investigating the ionic nature of FeO-SiO2 melts, Simnad, Derge, and George4, found the anode current efficiency, C,, as calculated from iron anode weight loss, was temperature invariant and in general increased with SiO2 concentration. The authors suggested the possible presence of electronic conduction to explain why C+ < 100 pct. Fig. 4 includes their results as curve (b). EXPERIMENTAL METHOD Apparatus—Fig. 1 is a schematic section of the electrolysis cell used in all the current efficiency runs. The melt was contained in an iron crucible that rested on an alundum ring. A centered silica tube came within 1 in. of the surface of the melt and initially served as a thermocouple well and then as the guide for the anode.

Jan 1, 1961

By E. A. Nesbitt

The important permanent-magnet alloys 15 years ago contained carbon and depended upon it for their permanent-magnet properties. In recent years great advances have been made in a number of new alloys substantially free of carbon. These include Remalloy,&apos; an alloy of iron, cobalt, and molybdenum, the various iron-nickel-aluminum alloys of the Mishima2 type, and the more recent Alnico V3 in which the best properties are developed by heat-treating in a magnetic field. The Mishima and the Alnico types of alloys are very brittle and after casting must be ground to size. This article describes a permanent-magnet material4 that can be machined as cast, and when handled with some care can be rolled to thin sheet and drawn to fine wire. Optimum magnetic properties are developed by a simple heat-treatment, and at this time the ductility of the alloy disappears. If the cast alloy is heat-treated without cold-working the mag netic energy product is about 1.0 X 106. This material is called Vicalloy I (pronounced vicalloy, V for vanadium, I for iron, and C for cobalt). When the alloy is first hot-worked and then considerably reduced in area by cold-swaging, drawing or grooved rolling, it is found that after heat-treatment the magnetic energy product measured in the direction of previous extension can be increased to 2.0 to 3.5 X 106. These higher values have been obtained only after reductions in area of 75 to 95 per cent, and since the material hardens considerably during working, the reduction ordinarily can be accomplished only in fine wires, although larger sizes can be reduced by the use of powerful machinery. When the material has been cold-worked in such a manner as to improve its energy product substantially, it is called Vicalloy 11. Commercial use of Vicalloy has been made in the recording of speech. Tape 0.002 by 0.050 in. has been found superior in quality to all others tried, and is now used in the Western Electric Mirrorphone 5 In a variety of forms Vicalloy I or I1 is useful in many laboratory instruments, and in experiments in which the sizes and shapes required cannot be obtained with the other more brittle permanent-magnet materials. In 1936, during a study of other age-hardening magnetic systems, it occurred to the author that some of the iron-cobalt-vanadium alloys might be suitable for permanent magnets. The proportions of iron, cobalt, and vanadium were varied and a range of alloys of particular interest was found, as shown by the indicated area in Fig. I. The limits of this range of composition are 30 to 52 per cent iron, 36 to 62 per cent cobalt, and 4 to 16 per cent vanadium. The compositions indicated by points outside this area were also tested. Preparation and Properties OF Vicalloy I The alloys were usually cast in graphite molds into bars 3/4 in. in diameter and

Jan 1, 1946

By F. S. McNicholas

IN the writer&apos;s opinion the term "block caving" has been rather loosely applied to a general principle of mining, and therefore detailed classification of caving methods and draw, together with the characteristics required for each method, will fill a desired need. Selection of caving method should be made only after a study of all governing conditions, such as size of orebody, lateral and vertical extent of ore-body, attitude, treatment demands, possible resultant pressures, and cost and profit comparison of methods. Successful caving methods can be classified under six main headings: (1) Full-protected block caving, (2) semi-protected block caving, (3) unprotected block caving, (4) full-panel caving, (5) half block-panel caving, (6) block-panel caving. The methods and factors governing choice of method are shown in Table I. Full-protected Block Caving Full-protected block caving consists of develop-ing, undercutting, and drawing to exhaustion a block of ore of predetermined size without coordination of mining or draw with adjoining areas. The block is mined and drawn as an independent unit (Fig. 1). Full-protected block caving demands that mining and draw cannot be done against unconsolidated capping in adjoining caved and exhausted blocks. Two sides of block are against solid. Caved capping must be allowed to consolidate for a suitable period, usually not less than one year. Pillars may be left in lieu of consolidated capping (Fig. 2). The advantages of full-protected block, caving are: (1) A definite area is developed, mined, and drawn as a unit so that all work may be completed, the block drawn to exhaustion in the minimum length of time, and the area then abandoned. (? Production is not restrained because of coordina1, on with adjoining areas. (3) Records of draw and caved reserve of ore are good. Upon abanwnment of the block, accountability for production is closed out with no carry-over to adjoining areas. The disadvantages of full-protected block caving are: (1) Side dilution from the draw adjacent to the consolidated capping may be serious, particularly where capping does not consolidate sufficiently in the allotted time. (2) Boundary weakening is needed on the solid sides of the block except in weak rocks. (3) Maximum cantilever and compression effect to aid caving and fragmentation may not be secured since the draw should proceed from the solid to the consolidated capping to minimize side dilution. However, undercutting from the loose (caved capping) to the solid with a slight initial draw in the same manner will develop cantilever effect. (4) A period of at least one year, more is usually desirable, must be allowed for caved capping ,to consolidate before mining the adjoining block, depending upon the characteristics of the capping. (5) Capping may not consolidate sufficiently in the time that can be allowed. Full-protected block caving is indicated where: (1) The ground is weak and heavy and workings

Jan 1, 1952