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By C. W. Spencer, Che-Yu Li, R. J. Knight

The usual reaction product for the monotectic reaction in the Bi-Se system consists of rod -shaped particles of selenium-rich liquid embedded in a single crystal matrix of At certain crystallo-graphic orientations of the matrix with respect to the reaction interface, more complex shapes are as -sumed by the liquid particles. This reaction has been examined at different growth rates and relative crystallographic orientations of the matrix with respect to the reaction interface. The uhriation in auerage particle size of the liquid phase with reaction rate has been determined at one crystallograpIzic orientation of the matrix. On a plot of logarithm of average particle diameter vs logarithm of reaction rate, data points for crystals grown at rates of 10- to 1.0 cm per hr fall near a curve of slobe -0.4. MONOTECTIC reactions in binary alloy systems are reactions of the eutectic class in which, as the system is cooled through the three-phase reaction isotherm, one liquid phase (L) decomposes to a solid phase and another liquid phase (LII).' A partial phase diagram, as taken from Hansen, showing the monotectic reaction in the Bi-Se system is given in Fig. 1. This diagram specifies the monotectic point at 618°C and 72 at. pct Se, and the monotectic reaction products as the intermetallic Bi Se3 and a liquid (LII) which contains approximately 98 at. pct Se. At a lower temperature, 217°C, this liquid may undergo a eutectic reaction in which the reaction products are BizSe3 and crystalline selenium. However, under conditions of rapid cooling, or quenching, from above 217°C, this selenium-rich liquid may be partially retained to room temperature in an amorphous or glassy state. The intermetallic BizSe3 is rhombohedral, of the space group jm;' however, for convenience it is usually represented by a hexagonal struture. A pronounced plane of cleavage, which lies perpendicular to the main axis of the rhombohedral unit cell or parallel to the basal plane of the hexagonal cell, exists in the structure. The usual monotectic reaction product consists of rod-like particles of LII embedded in a single-crystal matrix of BizSe3, although at certain crystallographic orientations of the matrix BizSe3 other more complex shapes are assumed by LII. A similar rod-like, or cylindrical, morphology for the carbide phase has been reported by westbrook7 in the a Cr-Crz3Ce eutectic structure. In this paper the morphological characteristics of the LII particles, as retained to room temperature, have been examined under conditions of varying growth rate and crystallographic orientation of the matrix BizSe3 with respect to the growth direction. EXPERIMENTAL PROCEDURE Alloy specimens corresponding to the monotectic composition, 72 at. pct, or 50 w pct Se, were prepared from 99.999 pct pure bismuth and selenium obtained from the American Smelting and Refining Co. The two elements, corresponding to a total specimen weight of approximately 30 g, were encapsulated in 13 mm OD Vycor tubing under a vacuum of 5 x X mm of Hg. The capsules were suspended on a fine platinum wire in a Bridgman-type furnace which exhibited a temperature gradient of

Jan 1, 1963

By R. G. Gifkins

Mean boundary migration depended linearly upon creep extension under various conditions. Prolonged annealing or air-casting increased the proportion of immobile boundaries at a given stage of tests. Grain growth during annealing followed a power law. The linking of migration and sliding in creep and models for migration are examined; activation energies are calculated from these models. Segregation of oxygen to boundaries appears to be a controlling factor. THE idea that boundary migration and boundary sliding during creep are linked has often been suggested,'-5 especially when evidence has been obtained for an alternation between the two processes. In simple bicrystals sliding can occur without any migration6 but in more complex bicrystals7 it is observed. McLean' and Couling and Roberts 5 made measurements of both sliding and migration; McLean concluded that there was no linking of the two processes whereas Couling and Roberts supported the idea. McLean' also developed a model for migration during creep and annealing. The present work was initiated as part of a study of the recrystallization of lead during creep9 but has been extended to examine some aspects of the mechanism of migration. MATERIALS AND METHODS Specially refined high-purity lead* was used; the total of impurities, excluding oxygen, was 0.0008 wt pct. Oxygen was removed as far as possible by melting in vacuo, treating at 550" to 600°C with hydrogen and then casting at 450°C under a vacuum of 10-2 mm Hg; the oxygen was then believed to be 0.00005 wt pct. Specimens were made from extruded strip and then annealed at the required temperature in an air oven, controlled to 5 lac. They were then polished in a mixture of acetic acid and hydrogen peroxide. At this stage some specimens were etched to give grain contrast and their grain sizes determined by the intercept method. Migration of boundaries during creep was measured on the surface of polished (not etched) specimens, directly loaded at room temperature (22°C) or 50°C (52"C) to initial stresses of 300 to 700 1b per sq in. Twenty six vacuum-cast hydrogen-reduced specimens were used and, in addition, two specimens were from material air cast after hydrogen reduction ("partial" air cast) and two from air-cast material not treated with hydrogen ("full" air cast). Duplicates were made in the majority of tests. At intervals through the creep tests, specimens were unloaded and the migration measured, normal to the direction of migration at the point of measurement, for each boundary along standard traverses. Usually between 110 to 180 boundaries were measured at each of some twelve stages of the tests. Migration was measured on the projected image (X100) using prism illumination. Fig. 1 illustrates the method of measurement and shows the kind of variation of migration found from boundary to boundary and along particular boundaries. Fig. 2 gives an example of more extensive migration. The mean value of distance migrated was generally reproducible to *10 pct but occasional points gave a scatter of *20 pct. The correctibn applied by McLean8 to allow for the contribution sliding makes to the apparent distance of migration could not be used, for the sliding at most boundaries was too small to measure with the equipment available. There were two reasons for supposing the correction unnecessary in the present work;

Jan 1, 1960

By John J. Gilman

BECAUSE of their layerlike structure, zinc crystals exhibit strong anisotropies for almost all physical and chemical properties. This should, and indeed does, greatly influence the plasticity of zinc for various crystal orientations. At low temperatures, the investigator of this plastic anisotropy is plagued by the great variety of deformation modes that operate. However, at high temperatures (250° to 419°C) only two deformation modes predominate: basal (0001) and prismatic (1010) glide. Furthermore, since strain hardening is virtually absent at high temperatures, the plasticity for these two modes of deformation can be very simply described by means of two equations of state. It is the purpose of this paper to describe the experimental behavior of basal and prismatic glide in zinc crystals, and to interpret this behavior in terms of other physical properties (in particular, the thermal expansion coefficients and the elastic constants) using the theory of dislocations. Fig. 1 defines the two planes of the zinc structure that will be discussed. Glide occurs very readily on the basal planes at all temperatures, and there is a very large literature on this subject. Much of the literature has been reviewed by Schmid and Boas;' it will not be reviewed here. Kolesnikovl was the first to show that if basal glide is circumvented by stressing a zinc crystal parallel to the basal planes (giving zero shear-stress on the basal planes) then, at temperatures above about 320°C, glide on the first-order prism planes occurs. His results have recently been confirmed by Cahn, Bear, and Bell." These previous workers have established the existence and crystallographic elements of prismatic glide; the present paper is concerned with the stress, strain rate, and temperature relations of prismatic glide as contrasted with basal glide. Experimental Methods The crystals were square ones, 6x6 mm, that had been grown in precision Pyrex tubes by a method that is described in detail elsewhere.' Most of the crystals were 99.999+ pct Zn (New Jersey Zinc Co. CP grade). Some were alloyed with 0.1 -+-0.005 atomic pct Cd, and chemical analysis showed that almost all of the added cadmium persisted through the crystal-growing process. For measurements of nonbasal glide, crystals were oriented with their basal planes parallel to both the rod axis and one of the flat faces of the square cross section. However, the orientation of the close-packed directions [1210] with respect to the rod-axis was variable. For basal glide measurements, the angle between the basal plane and the specimen axis was 35". The orientations were measured by the Gren-inger back-reflection X-ray method. The problem of finding a suitable method of gripping the crystals was the most serious experimental obstacle that arose. Because of the large plastic anisotropy of zinc, the usual gripping methods were unsatisfactory. Some methods that were tried were: high melting-point solder, making heads on the ends by locally melting a crystal, and electroplating nickel on the ends to form enlarged portions. For all these methods, the regions of the grips were weaker than the crystals themselves. Finally, two methods were decided upon: bend tests and direct machining of tensile specimens. In the bend tests, specimens were loaded as simple beams so that gripping was not a problem. The beams were 1 in. long and the axis of bending was parallel to the hexagonal axis of the crystals. For the crystals that were machined into tensile specimens, brass bars with slots in them were used to support the crystals, and thereby minimize the distortions due to machining. The crystals were glued into the brass bars with plastic cement which was later dissolved away with acetone. See Fig. 2, left. No clamps were used near the crystals and the machining was done using a milling machine with a fly-cutter. The tool bit was very sharply pointed to minimize burnishing. The feed was less than 1 mil per cut. The depth of cut was 2 mil for roughing cuts, and % mil for the finishing cuts. This machining method produced surface layers of tiny recrys-tallized grains only 2 to 3 mil deep, and the bodies of the crystals were not measurably disturbed. After the crystals had been machined and removed from the brass holders, they were chemically polished until about 5 mil had been removed from all their surfaces. The polishing reagent consisted of equal parts of concentrated HNO,, 30 pct H3O and ethyl alcohol; it is described in detail elsewhere." A typical crystal is shown in Fig. 2, right. The I-shaped faces are normal to the hexagonal axis of the crystal; otherwise the projections at the ends would simply shear off when the crystal was loaded. The cross section in the 2?-in. gage length is 0.215x0.115 in. It was found that the polished

Jan 1, 1957

By Peter N. Calder, G. H. Blackwell

The development of an open pit slope monitoring system, from equipment selection and justification to complete computer data storage and analysts, Is described. Methods of overcoming the Limitations of the electronic transit/distance measuring device and survey system selected are discussed. Results of the monitoring program showed that blasting was a major cause of Instability, and, after much experimentation, suitable blast patterns for mine production and pit wall integrity were designed. The experiences gained with double benching 'and wall cleanup procedures are discussed . The monitoring program also indicated that water was a contributor to instability, and methods of dealing with water In a rock with a low storage coefficient and transmissibility are described. Because of the danger of falling rock, photogrammetric methods are used for joint mapping and analysis, this work being contracted out. Joint strengths are measured on-site using a portable shear tester. Finally, a discussion of a complex failure is given.

Jan 1, 1983

By R. Kossowsky

BRIDGMAN has listed five possible transitions in bismuth at 25°C which were observed as volume changes. He was unable however to detect the last three transitions by electrical-resistivity changes. Kennedy and LaMori have verified the pressures at the Bi 1-11 and Bi 11-111 transitions. They suggested however that the 125-kbar transition previously reported by Bundy3 actually corresponds to the 90,000 kg per sq cm transition observed by Bridgman.1 Jura4 reported a well-defined drop in resistivity at 92 kbar obtained by a four-lead method. The Bi 111-IV and Bi IV-V transitions have not been reported in any of the above-mentioned references.'-' Bundy3 observed a small dent in the low-temperature boundary of the Bi Vll region which is consistent with the presence of a 111-IV boundary. Zeitlin and Bray-man5 were the only ones to report small but well-defined drops in resistance of bismuth at 44.0 and 63.8 kbar, corresponding to Bridgman's 111-IV and IV-V transitions, respectively. High-purity (99.99 pct) 0.020-in.-diam 0.5-in.-long bismuth wire was used to calibrate the Uniram tetra-hedral high-pressure apparatus used in the present work. The bismuth phase changes at 25°C were correlated with changes in electrical resistance as a function of pressure. The output of a sensitive bridge constructed of carbon resistors and kept at a constant temperature of ±°C during the measurements was fed to the Y axis of a MoseleyX-Y recorder and the X axis was used for time scans. Specimens were pressurized using a hydraulic press with maximum capacity of 200,000 lb. Load was applied in increments of 2000 lb and held for about 3 min. The resistance was recorded at the end of this time period. Good contact was established below 20,000 lb. Typical recorder charts are reproduced in Figs. 1 and 2 which show that resistance fluctuations were practically nil during each time scan. Well-defined discontinuities in resistance were observed at 58,000 and 82,000 lb, Fig. 1. Two small but definite "blips" are noticed at 92,000 and 122,000 lb, Fig. 2. At 156,000 lb another drop is observed which

Jan 1, 1967

By Milton Fies

ALTHOUGH pig iron from iron ore and red cedar charcoal preceded the mining of coal by many years, for tradition says that Alabama iron was used to shoe the horses of Andrew Jackson's soldiers, coal was not produced until 1830. In that year, coal was mined in Tuscaloosa County, in the vicinity of what is now the University of Alabama, and shipped on flat boats (obviously during the wet season, for there were many shoals) down the Warrior River to Mobile. About that time, the first railroad, the Decatur & Tecumseh, was being constructed in northern Alabama to overcome the obstructions to freight traffic caused by the now well-known Muscle Shoals in the Tennessee River. This railroad was patterned after a railroad at Mauch Chunk, Pa., which was used for hauling anthracite from the Panther Creek valley. The Alabama railroad, which required about four years to complete, was 46 miles long and was used solely for the transportation of cotton. Although it was a failure, it demonstrated the practicability of the undertaking, and the succeeding railroads, which were begun in 1834, 1848, 1852, and 1853, added immeasurably to the development of the coal resources of the state. Between the years 1830 and 1860, practically all the coal mined in the state was dug from the outcrop near the river or from the river beds, and shipped by boat to Mobile. Transporting coal down the Warrior River was one of great risk, required much skill, and frequently had heavy losses. It is recorded that this coal was sold to the gas company in Mobile in 1844; it was most likely mined from the Black Creek Seam. In 1914, on the completion of Lock 17, the Warrior River became a navigable stream from 9 miles above Cordova, Ala., to Mobile and offers a great opportunity for the future development of the coal resources of the state.

Jan 9, 1924

By S. A. LoPilato, J. T. Smith

SEVERAL techniques have been evaluated for cooling the throat area of rocket-nozzle inserts to prevent erosion or fracture of the inserts during exposure to high operating temperatures and pressures. Self-cooled composites, such as infiltrated tungsten, have shown considerable promise for these applications. These composites can be fabricated by infiltrating the refractory matrix with a lower-melting metal or non-metal which is insoluable in tungsten. During firing, the lower-melting substance undergoes a series of continuous endothermic phase changes which absorb sufficient heat to maintain the nozzle matrix material at or below a safe operating temperature. At present, the state-of-the-art has reached a point where the refractory matrix density and microstruc-ture have been established as the critical parameters to be controlled for optimum self-cooled performance.'" Nondestructive testing has been utilized to ensure that porous tungsten billets were of uniform density and free from cracks or other defects prior to fabrication into rocket nozzle inserts. Ultrasonic-velocity techniques have been employed because of their reliability and reproducibility. The purpose of this note is to present and interpret the test data developed for porous tungsten matrices. For evaluation purposes, tungsten powders with Fisher subsieve sizes of approximately 4 and 18 p have been obtained for study from four commercial sources: the General Electric Co., Wah Chang Corp., Fansteel Metallurgical Corp., and Kennametal, Inc. Porous tungsten matrices were fabricated from the powders by hot pressing in induction-heated graphite die assemblies. Typical billets ranged from 3 in. diam, 2 in, high to 5 in. diam, 5 in. high. The ultrasonic-velocity measurement technique employed was through transmission, pulse echo at a frequency of 1.0 mc using matched barium titanate crystal transducers. The testing equipment included a pulsed ultrasonic generator, an amplifier, a specimen holder, and an oscilloscope, as shown in Fig. 1. The porous tungsten thickness was measured to i 0.0005 in, with precision micrometers while the oscilloscope achieved 0.02 psec time measurement accuracy. The time for a sound wave to pass through the billet, the bulk wave velocity, was calculated to 0.5 pct using Eq. [l]: V-} where V = bulk wave velocity, in. per psec, T = specimen thickness, in., and / = time, psec. To develop inspection standards, the bulk density of a porous tungsten billet was determined by the ASTM water-immersion technique.3 The ultrasonic-velocity measurements were completed at seventeen positions for each billet and averaged to develop a characteristic standard velocity for a particular tungsten powder at several density levels. A plot of ultrasonic velocity vs density is presented in Fig. 2 for six different tungsten powders. This graph has been established as

Jan 1, 1967

By B. M. Larsen, L. S. Darken

Some years ago we collated all laboratory data then available to us on the distribution at equilibrium of manganese and of sulphur between metal and simple slags, and used the results in setting up an equation, which proved to be in accord with determinations of the distribution ratio of manganese and of sulphur between liquid steel and open-hearth slag, over a wide range of operating conditions. We now present an outline of our calculations and inferences on these two closely related questions, which are of especial importance because of the advisability of conserving manganese wherever possible. In general, our results show that in the open-hearth furnace equilibrium between metal and slag, with respect to both manganese and sulphur, is substantially attained during the finishing period of the heat, or in about a half hour to an hour after any additions were made. This implies that the end result will be identical whether manganese is added as alloy or metal to the liquid steel or as oxide to the slag. The proportion of total manganese retained by the steel is favored: (I) by use of the minimum amount of lime, consistent with other operating limitations, required to give a lime-silica ratio of about 2.4, which usually corresponds to a minimum practical slag volume; (2) by a high concentration in the slag of MnO relative to FeO; (3) by high operating temperature. Absorption of sulphur by the slag from the liquid metal is favored: (I) by large slag volume; (2) by a high concentration of active (or "free") lime and of manganese oxide dissolved in the slag; (3) by low concentration of silica, iron oxide, and phosphate dissolved in the slag. Distribution 02 Manganese between Slag and Metal at Equilibrium On the basis that the distribution of manganese between liquid steel and slag is controlled by the reaction FeO + Mn -& MnO + Fe [A] slag metal slag metal the distribution at equilibrium, at a given temperature, is expressed by the equilibrium constant for this reaction, which is defined as K,, _ aMnO' afe aFeO ' aMn where a is the activity of the molecular species denoted by the subscript. The activity of each of the several components, although it is not known precisely, is approximately equal to the concentration of each component expressed as its mol fraction; that is, as the ratio of the number of mols of the given component to the total number of mols of all the molecular species present in the metal or slag, as the case may be. Moreover, since the activity, or concentration, of iron in the liquid metal is in fact substantially constant, the term afe may be combined with K" to give a new constant K'. Making these changes, 7

Jan 1, 1942

By B. M. Larsen, L. S. Darken

Some years ago we collated all laboratory data then available to us on the distribution at equilibrium of manganese and of sulphur between metal and simple slags, and used the results in setting up an equation, which proved to be in accord with determinations of the distribution ratio of manganese and of sulphur between liquid steel and open-hearth slag, over a wide range of operating conditions. We now present an outline of our calculations and inferences on these two closely related questions, which are of especial importance because of the advisability of conserving manganese wherever possible. In general, our results show that in the open-hearth furnace equilibrium between metal and slag, with respect to both manganese and sulphur, is substantially attained during the finishing period of the heat, or in about a half hour to an hour after any additions were made. This implies that the end result will be identical whether manganese is added as alloy or metal to the liquid steel or as oxide to the slag. The proportion of total manganese retained by the steel is favored: (I) by use of the minimum amount of lime, consistent with other operating limitations, required to give a lime-silica ratio of about 2.4, which usually corresponds to a minimum practical slag volume; (2) by a high concentration in the slag of MnO relative to FeO; (3) by high operating temperature. Absorption of sulphur by the slag from the liquid metal is favored: (I) by large slag volume; (2) by a high concentration of active (or "free") lime and of manganese oxide dissolved in the slag; (3) by low concentration of silica, iron oxide, and phosphate dissolved in the slag. Distribution 02 Manganese between Slag and Metal at Equilibrium On the basis that the distribution of manganese between liquid steel and slag is controlled by the reaction FeO + Mn -& MnO + Fe [A] slag metal slag metal the distribution at equilibrium, at a given temperature, is expressed by the equilibrium constant for this reaction, which is defined as K,, _ aMnO' afe aFeO ' aMn where a is the activity of the molecular species denoted by the subscript. The activity of each of the several components, although it is not known precisely, is approximately equal to the concentration of each component expressed as its mol fraction; that is, as the ratio of the number of mols of the given component to the total number of mols of all the molecular species present in the metal or slag, as the case may be. Moreover, since the activity, or concentration, of iron in the liquid metal is in fact substantially constant, the term afe may be combined with K" to give a new constant K'. Making these changes, 7

Jan 1, 1942

Jan 1, 1887

By Henry Fay

LAWRENCE ADDICKS, New York, N. Y., (communication to the Secretary *).-There are two points regarding gun erosion on which I want to say a few words: The first is about the analogy to hardening of wire by drawing and the second the possible role played by thermal conductivity of the metal. The ductile metals do not necessarily become brittle when cold-worked as it is possible to draw copper from 3. in. in diameter soft rod down to the finest hair wire without annealing. This results, as stated in the paper, informing a hardened core with a very hard skin. The electrical conductivity is depressed some 3 per cent. and the tensile strength nearly tripled. A soft copper wire 0.08 in. in diameter and 6 in. long may be twisted 150 or more turns before the wire will snap under torsion. A hard-drawn wire will break after perhaps a dozen twists, the skin breaking down at one spot. Just wiping the wire with a cloth clamp with dilute nitric acid has a remarkable effect in increasing the number of twists without appreciably lowering the tensile strength, showing the skin to be very thin. On the other hand, pickling the rod, from which the wire is to be drawn, in dilute nitric acid also greatly increases the number of twists which can be applied to the resulting wire. This indicates that the copper oxide scale produced when the wire bar is rolled hot is more or less rolled into the rod and may have much to do with the skin effect. We also know that if the conditions of drawing are not correct, the heat of deformation in the die may produce quite an annealing effect. The application of this analogy to what occurs in a gun to produce the effects noted offers some difficulty. The second point is that as the temperature of the surface of the gun bore has undoubtedly a great deal to do with the amount of erosion, one natural remedy would be to conduct the heat away fast enough to keep this temperature within desired limits. This brings up the question of the thermal conductivity of the metal of which the gun is made. We know that the conductivity of pure metals is greatly altered by alloying and that the alloy is usually, though not always, lower in conductivity than the metal before alloying. This is interesting when it is considered that the high-nickel and manganese-steel alloys show greater erosion as stated. Would it not be instructive to study the question from the point of view of heat conducted away from the eroded surface?

Jan 3, 1917

By M. B. Bever, A. M. Reti, A. K. Jena

The results of this investigation show that in the system SnTe-PbTe l) the solid solutions have small exothermic heats of formation relative to the binary compounds, 2) solid-solution hardening is almost absent, 3) the tin and lead atoms are .randomly distributed on the sublattice occupied by them and do not undergo an ordering transition during a thermal treatment designed to promote such a transition, and 4) the lattice parameter changes linearly with composition. These findings suggest that the solid solutions of tin telluride and lead telluride approach ideal behavior. THE binary compounds SnTe and PbTe form a continuous series of solid solutions.' Information on several physical properties of these solid-solution alloys has been published.1"3 In the work reported here, the heats of formation, microhardness, and lattice parameters of these alloys have been measured and the possibility of an order-disorder transition has been investigated. Order-disorder transitions occur in some solid solutions of binary compounds. In the system Bi2Te3-BizSes, for example, the electropositive bismuth atoms and the electronegative tellurium and selenium atoms always occupy separate layers. In the disordered alloy Bi2Te2Se, the tellurium and selenium atoms are randomly distributed on the layers occupied by them, while in the ordered alloy they occupy distinct layers.4 The NaC1-type (Bl) structure of SnTe-PbTe alloys consists of two sublattices, one of which is occupied by the electropositive tin and lead atoms and the other by the electronegative tellurium atoms; any ordering would be expected to occur in the sublattice occupied by the tin and lead atoms. PREPARATION OF SPECIMENS Polycrystalline specimens of PbTe and Sn1-xPbxTe (x = 0.25, 0.50, and 0.75) were prepared by melting stoichiometric amounts of lead (99.999 pct), tin (99.98 pct), and tellurium (99.999 pct) in evacuated and sealed Vycor tubes. Because of the deviation of tin telluride from the stoichiometric composition5 this compound was prepared by melting 49.8 at. pct Sn and 50.2 pct Te. The tubes containing the melts were quenched into water; the solidified ingots were removed from the tubes and annealed for 2 weeks in vacuum (PbTe approximately 100°C below its melting point, the three alloys 100°C below their solidus tem-

Jan 1, 1969

By R. W. Waterfill

MANY existing ore deposits of valuable metals have been worked out in their upper surface levels and the continued productivity of these mines is dependent on their extension to greater depths in the earth. The maximum depths at present reached are about 6000 to 8000 ft. below the surface, with no evidence of an impoverished ore vein. These mines are widely distributed; some of the best known are in South Africa, Brazil, India and in the western sections of the United States. Among the factors which increase the difficulty of working these mines at increasing depths are hoisting, rock pressure and temperature. The manner and effectiveness with which these problems are met will, no doubt, determine in a large measure the ultimate depths to which any mine can be profitably worked. The most critical of these three factors at present is the increase in temperature with depth. The high temperature and humidity in many of these mines at present is severely detrimental to the health of the workers and greatly hampers their efficiency. Some have almost reached a condition in which the human system cannot survive. The problems involved in the cooling and ventilation of mines have all been ably analyzed and presented in previous articles. For this reason, only a resume of conditions affecting the cooling and conditioning of deep and hot mines will be given in this paper before attention is directed to possible methods of improving atmospheric conditions in the working levels.

Jan 1, 1929

By W. K. Godfrey

The highest compressive strength cement has the highest bond strength in tests in which the cement is subjected to a confining pressure. After perforating, the bond strength is reduced to nearly zero when the pipe is supported by weak cement. Perforating does not affect the bond strength, however, when the pipe is supported by strong cement. Pipe supported by weak cement is damaged by perforating with expendable capsule jets, but is not damaged by perforating with the hollow carrier gun. High strength cements are recommended for oil wells that are to be perforated. Introduction The purpose of this work is to determine the effect of jet perforating on the bonding strength of oilwell cement at simulated down-hole conditions. Bond strength is a good criterion for determining the effectiveness of cement in performing its main function, i.e., that of isolating zones. According to the literature on the subject, the optimum cement strength for perforating is low and should not exceed 2,000 psi compressive strength. This conclusion was based on the appearance of bullet and jet perforations in neat and gel cements largely done in the absence of a confining pressure more than 15 years ago. Discussion Literature A relatively weak cement has been recommended in the literature as having optimum properties for perforating. In 1947, Oliphant and Farris tested bullet perforating of neat cements at various curing times.' Some of the tests were made at down-hole conditions. They reported that the optimum cement strength for perforating was about 2,000 psi compressive strength. Enlarged holes occurred when strength was too low, and the cement shattered and cracked when the strength was too high. In 1951, Morgan and Dumbauld tested bullet and jet perforating of neat and gel cements at surface conditions.' They reported that optimum cement has a compressive strength less than 2,000 psi. In their tests at atmospheric pressure, high strength cement shattered and cracked when perforated. Thus, the optimum cement strength was based on the appearance of neat and gel cement after perforating. In 1953, Clark showed a relation between cement strength and fluid shutoff.' He concluded that a 500 psi compressive strength is required for good fluid shutoff and that maximum bonding ability is developed at approximately 1,000 psi compressive strength. In 1964, Bell and Shore invalidated most of the conclu sions by the previous authors when they demonstrated that atmospheric pressure tests cannot be used to determine casing deformation and damage that will result from perforating under down-hole conditions.' They showed that the higher the hydrostatic pressure, the more restricted will be the expansion of gases generated by the charge. Less casing deformation and damage occurs under down-hole conditions than at atmospheric pressure. In recent work, Bearden et al. reported that jet perforating at surface pressure with the hollow carrier gun caused the cement sheath to shatter and crack.' The perforating, however, did not seriously affect the pressure required to leak past the casing cement bond. Only three cementing mixtures were tested, and presumably they had strengths in excess of 2.000 psi. Bearden et al. also reported that the hydraulic bonding strength increased as the compressive strength increased. Their hydraulic test showed that approximately 1,000 psi pressure is sufficient to break the casing cement bond for a well aged neat Portland cement sheath. Unfortunately, the tests were not run with a confining pressure, so Bearden et al. were merely measuring the strength of their outer 8%-in. casing. In our investigation, we measured the hydraulic bond strength of cement to pipe under a confining pressure and found that the bond strength was not limited to 1,000 psi. Cement Bond The bond strength is a good criterion for measuring the effectiveness of cement in performing its main function, that of preventing interzonal communication of fluids behind the casing. Measuring bond strength after perforating should be a good quantitative method of determining optimum cement properties, and should be a better method than that used by previous investigators,11 ' who simply observed the appearance of the cement after perforating.

Jan 1, 1969

By Alexander Knoll, Dwight L. Baker

THIS paper is a report on work undertaken to investigate the results and conclusions of Ravitz and Porter1,2 that galena freed of surface oxidation products and lead carbonate ("clean" galena) is waterrepellent, and that the action of xanthates in flotation is the action of a cleansing agent, enabling oxidized galena particles to expose a pure lead sulphide, water-repellent surface. The apparatus, in construction and use, was essentially that of Ravitz and Porter. The only significant modification introduced by the present authors was the substitution of a three-necked flask for the flotation cell as the "reaction vessel." Our procedure was to place 50 grams of freshly ground, minus 200-mesh galena in the reaction vessel, sweep out all molecular oxygen from the system with oxygen-free nitrogen, and proceed to wash the galena surface free of its oxidation products with repeated small portions of (I) ammonium acetate (500 c.c. of water, 200 grams of ammonium acetate) or (2) ammonium chloride, hydrochloric acid (2 liters containing 200 grams of ammonium chloride and 25 c.c. Of 1.18 sp. gr hydrochloric acid). The galena was next washed with many 100-c.c. portions of oxygen-free, distilled water. The galena was finally considered free of soluble salts when wash water that had been in contact with the mineral for at least 48 hr.* gave negative tests for: (x) lead ion with sulphide; (2) chloride with silver ion; (3) acetate with cuprous chloride, sodium chloride; and (4) ammonium ion with Nessler's reagent. Next 500 c.c. of potassium ethyl xanthate solution, free of dissolved oxygen, was run onto the "clean" galena particles. For this system there were determined: I. The wetting properties of the clean galena particles by shaking the reaction flask and noting the degree of mineral collection at the liquid-air interface. This was, of course, simply a qualitative test, but it proved adequate for our purpose. 2. The removal of xanthate ion from the potassium xanthate solution on being shaken with the "cleansed" mineral. Xanthate concentrations were determined by iodine titration according to the methods of Taylor and Knoll.3 3. The pH of the xanthate solution after having been shaken with the "cleansed" galena. The pH was determined colorimetrically.4 The results of five experiments of the type mentioned above are given in Table x.

Jan 1, 1941

Jan 1, 1925

By W. Hodge, A. F. Haskins, R. M. Evans

Refractory boron compounds are shown to resist corrosion by molten zinc. Coatings were made from ferroboron and manganese boron by several methods: welding, hard facing, and pack diffusion; and techniques of coatings are very important. Mechanical failure of the diffusion coatings can be partially eliminated by applying them to type 416 chromium steels rather than carbon steels. Welded coatings made with a tungsten arc are better than those made by other welding methods. Sintered compacts of mixtures of iron and chromium borides developed strengths of about 30,000 psi. They resisted corrosion of zinc at 600°C and oxidation at higher temperatures. MOLTEN zinc rapidly attacks common metals of construction. The rate of attack is greatly amplified at temperatures over 500°C. However, there are many applications where it is necessary, or at least advantageous, to use metal construction, such as for galvanizing pots and zinc smelter equipment. Condensers and agitator linings used in continuous zinc smelting processes are eroded and corroded by violently agitated molten zinc. Pumps, tubing, and other parts to permit transfer of molten zinc would be desirable in many zinc handling operations. The development of metallic materials which are resistant to molten zinc also might permit its use as a heat-transfer medium in modern high efficiency power plants. In reviewing previous work on zinc-resistant metals, it was evident that most of the available data refer to corrosion at temperatures just above the melting point. Tungsten and high Mo-Fe alloys containing more than 80 pct Mo resist corrosion by molten zinc.', ' Imhoff states that because chromium is not attacked by zinc, chromium plating improves galvanizing pot life." Nitrided cast iron has been used in die-casting machines' where the molten alloy is 96 pct Zn and 4 pct Al. Other metals that have been suggested as of possible value for zinc resistance are columbium, tantalum, and titanium.V he corrosion of steel by zinc has been discussed by many authors,z, "2 None of these materials resisted corrosion by molten zinc at the temperatures used in this investigation, i.e., 600" to 700°C. I. Exploratory and Resistant-Coating Tests To make a study of zinc-resistant metals, exploratory tests were conducted to sort out roughly those materials which seemed most worthy of further development. This preliminary study included both solid metals and surface coatings. Exploratory Corrosion Tests in Molten Zinc—In initiating a study of this problem, numerous samples of metals and alloys were evaluated by dynamic corrosion tests made at 440 °C. Each metal was tested in its most readily available form, which, because of shape and size, was often unsuited for standard corrosion testing. The equipment used for dynamic corrosion testing of all materials, except in a few initial experiments, is shown in Fig. 1. Samples were tied to tungsten rods with tungsten wire, immersed in the zinc, and revolved at 12 rpm about the circumference of a 4 in. diam circle. Speed of travel was about 12.5 fpm. The molten zinc was protected from oxidation by an atmosphere of carbon monoxide, or, at a later period in the program, by a 9:1 mixture of nitrogen and hydrogen. When the effect of both molten metal and atmosphere was desired, the zinc level was lowered. Special high grade zinc was used in all of the corrosion tests. Corrosion losses for materials tested are shown in Tables I and 11. Whenever the materials were available in suitable form, the losses are reported in mils per year. It was recognized that weight losses on irregularly shaped specimens did not show the corrosion rate but the important consideration—poor resistance to corrosion—could be determined readily.

Jan 1, 1956

By S. K. Tarby, W. O. Philbrook

The rate of FeO and MnO reduction from silicate and aluminate slags by carbon-saturated iron is dependent on both slag composition and temperature. Owing to variable stirring rules during- the course of reaction, the reduction processes occur in two stages in stationary graphite crucibles. In the first stage the slirring caused by CO evolution results in forced convection conditions in the slag. As the boiling action subsides during reduction, the flow conditions within the system become those defined by natural convection. Analysis of the data by an unsteady-state penetration model indicates that the rate of reduction is controlled by the rate of cocur-rent flow of' cations and anions from the bulk slag to the interface during both stages of reduction. The hearth reactions of the blast furnace have been extensively investigated from the viewpoint of equilibrium by deductions from controlled laboratory experiments. However, the literature contains relatively few studies that have been directed toward the area of slag-metal reaction kinetics, and the majority of these have been concerned with the rate and mechanism of sulfur transfer between iron and slag. More recently, attention has turned to the kinetic factors in the reduction of oxides from liquid slags. One of the first investigations in this field was conducted by Dancy1 on the reduction of pure liquid FeO and pure liquid Fe3O4 by carbon-saturated iron. The integrated form of the rate equation indicated that the reduction of FeO was of the first order up to 80 pct reduction. Over the initial 30 pct of reduction, the magnetite reaction was also interpreted as a first-order process. The rates of reaction were extremely rapid as indicated by a 30 pct reduction of the liquid magnetite in a time interval of about 1 to 2 sec. Phil-brook and irkbbride' studied the reduction of FeO from a lime-alumina-silica slag by carbon-saturated iron and solid graphite in stationary crucible assemblies. With the use of the differential form of the rate equation, the rate of the reduction reaction was found to be proportional to the second power of the concentration of the reactant FeO for both the slag-metal and slag-graphite reactions. These authors presented a number of comments in an effort to explain the difference between the molecularity of the above reaction and the observed second-order relation. One such argument, recently extended by Wagner,3 was that the rate-limiting step may well be one of transport control. A complete discussion of the proposed mass-transport control mechanism of this reduction reaction will be presented in a later section of this paper. Kinetic studies of the reduction of other oxide species, namely chromous oxide, titania, and silica, have also been reported. McCoy and philbrook4 used rotating crucible assemblies to investigate chromium reduction from Ca0-SiO2-A12O3 slags. First-order kinetic law was obeyed for the slag-metal reduction reaction as determined by the integration method of data analysis. Due to scatter of the data, any dependence of the rate constant on temperature or slag composition was obscured. Concentration-time data for the reduction of titania from blast-furnace type slags under reducing conditions were obtained by Delve, Meyer, and Lander.' The data were too few, however, for a formal kinetic interpretation. Kinetic data for the very slow reaction of silica reduction have been observed by McCoy and Philbrook6 and Fulton and chipman.7 The former experimenters found the reaction-rate constant for silica reduction by carbon-saturated iron to be 20 to 60 times less than the rate constant for chromium reduction. In their work on the reduction of SiO2 in mechanically stirred systems, Fulton and Chipman also found small values for the specific reaction rate and derived a high value for the energy of activation for the reaction. In both of these investigations, the reduction process was assumed to follow first-order behavior. schuhmann8 proposed that the rate-limiting step in this reaction is the diffusion of oxygen from the interface through a boundary-layer film to the bulk metal phase, and Rawling and Elliott9 have reported experimental confirmation of this hypothesis for temperatures below 1600°C. Turkdogan et a1.10 have also concluded that the rate of reduction of silica is a slow process and controlled by the diffusion of oxygen in the metal, but only in the absence of carbon monoxide bubbles at the slag-metal interface. In the presence of bubbles, achieved either by injecting carbon monoxide at the slag-metal interface or by blowing it through the metal and slag, these investigators found a rather rapid reduction of silica which appeared to be controlled by an interfacial reaction involving the de-sorption of silicate ions from the slag-metal interface to the metal phase as silicon and oxygen atoms. In view of the unresolved nature of the kinetics of FeO reduction and the lack of kinetic data for the manganese reaction,

Jan 1, 1968

By C. H. Mathewson, Kent R. Van Horn

Copper and the copper-base solid solutions readily form twin crystals when plastically deformed at a suitably elevated temperature or annealed after cold deformation. In fact, no feature of the microstructure of these materials is more prominent or characteristic than these straight-sided bands or simple lines of division which sometimes come from groups of thin polysynthetic lamellae, penetrating part way or wholly through the parent grain substance, but often divide the grain into a few or perhaps only two crystallographically related parts. Nearly always the bands as seen in the usual microscopic examination of a specimen come into vivid contrast with the adjacent crystalline material owing to the inherent difference in orientation. Bands which under special conditions of orientation cannot be seen with vertically incident light are often visible under oblique illumination and, when this fails, contrasting effects usually may be obtained by using polarized light. There is no longer any doubt that these synthetic banded structures obtained in the ordinary course of working and annealing are due to twinning of the spinel type which was observed long ago in a number of metals crystallizing in the isometric system.' It has been customary in metallurgical literature to designate these synthetic twins, which grow into prominence during an annealing process, as "annealing twins" without regard to the actual mode of their formation, which is, indeed, obscure and with scant recognition of the fact that prior deformation is essential, no twins having been observed in metal of known unstrained history. This is questionable; especially in view of the fact that in a number of metals and minerals, reorientation into the twin configuration is known to occur as a result of a simple shearing mechanism along the recognized twinning planes and the

Jan 1, 1930

By T. E. Leontis

ONLY a limited amount of information has been published on the effect of thorium as an alloying ingredient in magnesium. McDonald13'2 showed that the addition of thorium in amounts up to 3 pct increases significantly both the ductility and the strength of rolled magnesium sheet. A recent publication by Sauerwald" indicates that thorium contributes strength and creep resistance at elevated temperatures to magnesium in both the cast and wrought states. The observations of Sauerwald are confirmed in this paper, which presents the results of a systematic study of the effects of compositional variation on the tensile properties, creep resistance, conductivity, density, and metallography of Mg-Th alloys containing up to 50 pct Th both in the sand-cast and in the extruded states. The effect of the addition of cerium to Mg-Th alloys is also reported. Experimental Methods The alloys studied in this investigation were pre.pared in small laboratory melts according to the melting practice described by Nelson4 as the crucible method. Electrolytic magnesium was used as the starting material to which the thorium* was introduced in metallic form. It was observed that the behavior of thorium in molten magnesium with respect to reaction with protective fluxes is similar to that of rare-earth metals. In order to obtain the highest possible alloying efficiency, it is necessary to use non-MgC1, fluxes and to apply all the precautions described by Marande6 for melting, alloying, and casting magnesium-rare-earth alloys. .Under these conditions it is possible to obtain an alloying efficiency in the range of 85 to 95 pct. The Mg-Th-Ce alloys were made with cerium of the highest purity available, not with the commercial product "misch-metal" which contains approximately 50 pct Ce. The total rare-earth content of this material was 97.1 pct, of which 0.3 pct was rare-earth metals other than cerium; the major impurities comprising the balance were iron and magnesium. The thorium and cerium contents of each alloy were determined chemically. Test bars 6% in. long with a 2% in. long reduced section of % in. diam were cast in sand molds using a four-baf pattern. In most cases, a 3 in. diam extrusion billet 10 in. long was cast in a steel mold from the same melt used for making the sand-cast test bars. For the higher thorium alloys, it was necessary to remelt the foundry scrap from the test bars in order to make the extrusion billets. The billets were scalped to a diameter of 2 15/16 in. and the ends faced to a length of 9% in. as limited by the size of the extrusion container. The alloys were extruded into % in. diam rod on a 500-ton direct-extrusion press. The details of the extrusion process are as follows: Billet preheat 925°F (2 to 16 hr) Container temperature 900 °F Die temperature 900°F Extrusion speed 10 ft per min Reduction ratio 36:1 Percent reduction 97.3 Alloys containing up to 10.2 pct Th were preheated at 925°F for 2 hr; all alloys with higher thorium contents were preheated for 16 hr. In order to establish the effect of extrusion temperature, billets of

Jan 1, 1953