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By Horace Pops

Martensitic transformation has been studied during cooling and heating in ß-phase Cu-Zn alloys to which small additions have been made of Ni, Ag, Au, Cd, Ga, In, Si, Ge, Sn, and Sb. The start and finish of the martensitic reaction and the variation of transformation temperature with third-element content were determined by electrical-resistivity measurements from alloys which had either constant zinc contents or constant values of electron concentration. All of the third elements, except nickel, lowered the transformation temperature if the results were plotted along the lines of constant zinc contents in each ternary system. A significant difference in the rate of lowering of the transformation temperature per atomic percent of the third element was observed for elements which had the same nominal valence. No systematic variation of transformation temperature with the valence of the third element was observed. It is suggested that the observed increase in transformation temperature for nickel-bearing alloys is due to the transfer of electrons from the conduction band of the alloy to virtual bound states. However, electron concentration is not the most important factor controlling the instability of the 0 phase. The transformation temperatures of the ternary alloys can be predicted from the following approxilnate expression: Ms (°K) = +3280 - 80 Zn + 8 Ni - 30 Ag - 12 Au - 140 Cd -90 Ga- 145 In - 80 Ge -175 Sn - 120 Si - 150 Sb MOST binary ß -phase alloys based upon the noble metals copper, silver, and gold are unstable at low temperatures and transform spontaneously by a martensitic reaction. This transformation has been studied recently in the ordered bcc ß'-phase Cu-Zn binary al1oys1,2 where the transformation temperature is below the room temperature and decreases with an increase in zinc content. It has been reported that the transformation temperatures can be raised above room temperature by small additions of a third element such as silicon3,5 or gallium,4,5 but no quantitative study has been made. The transformation temperature of different binary alloys can be altered by third-element additions. For example, it was shown that nickel and copper may have a large effect on the Ms temperature of CU-Al6 and Au-cd7 alloys. The present investigation was made to determine systematically the influence of various third elements on the martensite-transformation temperature of Cu-Zn ß-phase alloys. Since these alloys have an electronic origin,' alloy compositions were chosen so that the transformation temperatures could be determined at constant zinc contents or at constant values of electron concentration. I) EXPERIMENTAL PROCEDURE Ten ternary alloy systems were obtained by adding nickel, the noble metals silver and gold, and some B-subgroup elements to a Cu-Zn matrix. These are arranged according to their rows and columns in the Period Table as follows: Each ternary alloy was prepared by melting and casting weighed quantities of high-purity metals (99.99+ pct) in sealed quartz tubes under a partial pressure of helium to make a 4-g ingot. The molten alloys were shaken vigorously and then quenched in water. Since the weight loss was negligible, the compositions of the ingots after casting and annealing were assumed to be the same as the nominal compositions. The ingots were homogenized after casting in helium-filled Vycor tubes for 24 hr at temperatures between 750" and 810 C and quenched into brine. Metallographic examination revealed that all alloys were homogeneous, poly crystalline ß-phase alloys, and that the grain size was in the range 1 to 5 mm. Electrical-resistivity measurements were made to determine transformation temperatures of the ternary alloys during continuous cooling or heating. Transformation temperatures of the ternary alloys can be determined by electrical-resistivity measurements since the resistance of the martensitic phase is much higher than that of the 0' phase. The technique has been described previously in connection with a study of Au-Zn alloys.9 The reproducibility of transformation temperature was approximately ±6°C. II)RESULTS A hysteresis was always observed in electrical-resistivity curves and was usually less than about 12°C.

Jan 1, 1967

By R. H. McLean

Jet impingement produces two mechanisms to clean the bottom of a borehole during jet-bit drilling operations. One is an impact-pressure wave in the immediate area of jet impingement. The other is crossflow, which spreads across the bottom away from the pressure wave. Measurements of the vertical distribution of the cross-flow at several positions beneath a 4 3/4-in. tricone jet bit in a laboratory model show that the maximum velocity in the crossflow is directly proportional to the square root of the product of the rate of flow and the velocity of the jets through the nozzles (QV). Other measurements in the laboratory model show that gradients in the impact-pressure wave are directly proportional to the jet QV if the diameters of the nozzles are held constant. Consistency of the basic relationships through changes in the Reynolds numbers of the jets from 31,000 to 93,000 suggests that the laboratory results should be representative of typical flow in field operations having higher Reynolds numbers. Estimates of the impact-pressure waves under conditions other than those in the jet-bit model may be made by comparison with a less complex model—impingement of a jet against an unrestricted flat surface normal to the jet. Equations derived from current jet technology describe the wave in this simple system for a wide range of conditions. INTRODUCTION The efficiency of rotary drilling operations is strongly linked to the efficiency with which cuttings are removed. Cuttings remaining on the bottom of the borehole will impede further penetration by the bit until they are removed. Wasteful regrinding is prevented if the fluid circulated past the bit removes cuttings as rapidly as they are made. Most investigations of bottom-hole cleaning under bits have been concerned with the rate-of-penetration effects of bit type, nozzle configuration, fluid properties, pressure gradients and utilization of hydraulic horsepower. These investigations have shown that drilling muds, weighted to keep the pressure in the borehole greater than in adjacent formations and carrying material which forms a filter cake, apparently plaster cuttings against the bottom, making them difficult to remove. In addition to a demonstration of the factors causing poor cleaning, the most significant result of these previous investigations has been the increased use of jet bits accompanied by better hydraulic programs and better selection of drilling fluids. Undoubtedly, these practices have improved bottom-hole cleaning, but rates of penetration when drilling with muds are still often lower than would be expected with perfect cleaning." Although there is general agreement with the concept that increasing hydraulic energy at a jet bit often increases the rate of penetration by improving cleaning, research workers have differed as to the best criterion for evalyating hydraulics. Some lean toward maximizing the product of the rate of flow and the velocity through the nozzles (QV) others prefer to maximize the hydraulic horsepower at the bit;'"-' "till another says that neither criterion is universally suitable."' This controversy shows that conclusive field evidence has not established the superiority of either of these criteria. Analysis of the fluid flow which cleans the bottom should contribute to resolving the controversy. Impinging jets clean the bottom by creating two mechanisms capable of dislodging cuttings. One is the impact from the momentum of the jet and the other is the flaw parallel to the bottom away from the area of impingement. The impact force appears in the form of a pressure wave on the bottom and, in this paper, is called the impact-pressure wave. The flow parallel to the bottom is called crossflow. Fig. 1 illustrates these two mechanisms. This paper describes crossflow and the impact-pressure wave beneath jet bits and relates them to controllable parameters. Through these relations, criteria for use in designing hydraulics to achieve maximum use of the mechanisms of cleaning are derived. PROPERTIES OF CROSSFLOW CONCEPTS DEVELOPED IN PREVIOUS INVESTIGATIONS Concepts of scavenging the bottom by crossflow have been well discussed by Bobo, et al." They examine the means by which crossflow may create forces on cuttings and conclude that the cleaning action of crossflow can be increased by increasing the velocity of the flow stream close to the bottom. Using boundary layer theory, they indicate that a reduction in the viscosity of the drilling

Jan 1, 1965

By Raynor Linzey, Karl M. Busen

The formation of thin films of silicon oxide by anodic oxidation of silicon and the subsequent removal of these films by an etch is a process often used for the evaluation of concentration distributions Profiles) in silicon layers by the differential sheet conductance method. The accuracy of the resulting profile is very strongly influenced by the uniformity of the thickness of the reacted silicon. Normally, it would be expected that for a constant number of coulombs passed the thickness would be the same from oxidation to oxidation. Investigations show that in certain electrolytes, for a given number of coulombs passed through an n-type silicon sample, the thickness of the reacted silicon increased with increasing resistivity. Even for the same resistivity the thickness varied sometimes by a factor of 1.5. When an electrolyte was used which consisted of 10 pct water by volume in ethylene glycol with 4.0 g KNO per 1000 ml of solution, anodiza-tion at 5 ma per sq cm led to satisfying results. Short-time anodizations gave oxide layers of a higher apparent density than those experienced from thermally gown silicon oxides. THE functioning and the electrical characteristics of semiconductor devices are based upon the incorporation of "impurities" into a single-crystalline body of suitable material and on the concentration distribution (profile) of this impurity. The incorporation can be achieved by well-known processes as, for example, by diffusion, epitaxial growth, alloying, or ion implantation. Often the profile resulting from these processes is not known. A powerful tool to learn about a concentration distribution is given by the method of differential sheet conductance which employs successive four-probe measurements on a layer subjected to stepwise removal of thin sublayers. Differential sheet conductance vs position (or penetration depth) of a sublayer is plotted and a smooth curve is drawn through the data. From this curve the profile is then calculated. When the semiconductor material is silicon, the sublayers are removed suitably by anodic oxidation of the silicon and subsequent dissolving of the formed silicon oxide by an etch. The accuracy of the resulting profile is very strongly influenced by the uniformity of the sublayer thickness. Normally, it would be expected that, for a constant number of coulombs passed, the thickness would be constant from oxidation to oxidation. Investigations showed that for sublayers several hundred angstroms thick the reproducibility can be rather poor. Therefore, efforts were made to obtain a reliable technique for uniform removal. The present paper describes such a technique and certain phenomena which were encountered during the investigations. APPARATUS AND TECHNIQUE The first report on the investigation of concentration distributions, where for differential sheet conductance measurements thin silicon sublayers were removed from a diffused layer by anodic oxidation, was given by Tannenbaum. The author reports the removal of sublayers which for the most part were 400 thick. More advanced device designs now require much narrower layers. When it was tried in these laboratories to determine profiles within such layers, difficulties were encountered with respect to sublayers which by necessity had to be thinner than the ones reported by Tannenbaum. The apparatus used for the investigations is sketched in Fig. 1. Two cylindrical containers connected by a wide tube are filled with an electrolyte. The left container receives the cathode whereas the right container is closed at the bottom end by a sample support consisting of a Teflon base and a copper pedestal. The silicon sample (1 by 1 cm) is mounted to the pedestal embedded flush in the Teflon base using silver paint (Degussa) for electrical contact. Pyseal is applied to the edges of the sample to protect the copper pedestal from the electrolyte. The base is mounted to the container using a water-tight silicon rubber gasket. Fig. 2 gives a view of the sample support. The copper pedestal is connected to the positive side of a power supply operating at a constant current output (Kepco Model ABC 425M). The electrolyte which has been reported by Duffek et al. consisted of either 2 or 10 pct water by volume in ethylene glycol and 4.0 g KNO3 in 1000-ml solution. The electrolyte is best prepared

Jan 1, 1967

By R. W. Hertzberg, F. D. Lemkey, J. A. Ford

The effect oj unidirectional solidification upon the microstructural, crystallographic and mechanical characteristics of high -purity A1-A13Ni eutectic a1loy specimens has been investigated. varying the growth rate caused the morphology of the Al3Ni phase to gradually change from platelets to rods. In addition, the effect of increasing the rate of planar liquid-solid interlace movement is to decrease the Al3Ni rod diameter and inter-rod spacing. The platelets and rods grow approxinlately parallel to each other and are aligned in a faulted substructure. A single unique crystallographic relationship hetween the A1 and ASNi phases was found and may he descrihed as : interface {001} Al3Ni {331} Al and growth direction <010>Al3Ni || <110> Al The platelet interlace and the aligned rows of rods are both uniquely defined by the above statements. Alignment of the Al3Ni phase by unidirectional solidification has given rise to a threefold increase in strength over that exhibited by specimens with an as-cast microstructure. These results illustrate the possible use of this eutectic alloy as a zohisker -reinforced structure. It has been demonstrated by Winegard et al.,1 Kraft and Albrighht,2 Chilton and winegard,3 Chad-wick,4 Yue,5 Tiller,6 and others that a planar liquid-solid interface may be established in binary eutectic alloys by proper control of heat flow during the solidification process. The unidirectional movement of such an interface results in a eutectic mi-crostructure consisting of an essentially parallel array of the two phases over an entire ingot. Two dominant phase micromorphologies have been produced using this technique: that of substantially parallel alternating lamellae of each phase or long thin parallel rods of one phase imbedded in a continuous matrix of the other phase. While not all eutectics can be controlled in this manner, it has been shown that a "normal" eutectic may, under properly controlled conditions of purity, liquid and solid thermal gradients, and solidification rate, be forced to solidify with essentially parallel phase particles. Kraft and Albright2 have demonstrated that, when the growth rate is too rapid or when the thermal gradient in the liquid at the growing interface is too low, a layer of constitutionally supercooled liquid, formed by impurity build-up, will stabilize a cellular rather than a planar interface. The unidirectional movement of the cellular interface forms the macrostructure of eutectic colonies.7 Chilton,3 Chadwick,4 and Tiller,&apos; studying eutectics of zone-refined Pb-Sn, A1-CuAl2, Zn-Sn, and Cd-Zn systems, noted that in the absence of impurities a planar interface is stabilized even when rapidly solidified. Although it is generally agreed that impurities break down a planar interface to form the eutectic-colony macrostructure, at present the origin of the varying micromorphologies (i.c., plates or rods) in a given normal eutectic alloy is not completely understood. Tiller8 has predicted that the micromor-phology produced may be dependent on solidification rate (i.e., at fast rates a rodlike structure is preferred whereas at slow rates a lamellar structure should form), and also suggested that rod formation may be favored at large phase-volume ratios. yue5 has experimentally verified Tiller&apos;s prediction in the eutectic Mg-Mg17Al12 by observing a lamellae-to-rod transition with increasing growth rate where the phase-volume ratio was approximately 2.3:1. However, Hunt and chilton9 more recently unidirec-tionally solidified over a wide range of growth velocities six different eutectic systems with phase-volume ratios between 12:l and 2.7:1 and observed no lamellae-to-rod transition. chadwickl0 has proposed that the change in micromorphology in some eutectic alloys is due entirely to the presence of impurities and further states that the lamellar structure is the characteristic structure of pure eutectic alloys even when the phase-volume ratio is as great as 12:l. Kraft11,12 has shown that the parallel lamellae in certain eutectic alloys assume a unique crystallographic relationship during unidirectional growth. This preferred crystallography may be developed

Jan 1, 1965

By D. A. Elgillani, M. C. Fuerstenau

With either sulfonate or oleate as collector, quartz responds to flotation with moderate additions of calcium only at moderately high pH, where some portion of the activator has hydrolyzed to caOH+ . Calculations of the concentrations of various ionic and precipitated species of calcium and collectors suggest that the products of [(CaOH+) (RSO3)] and [(CaOH+)(01-)] determine whether flotation is obtained under specific conditions. Ion products on the order of 10-12 were calculated for both the sulfonate and oleate systems. The activating effect of calcium ion in nonmetallic flotation systems is of considerable interest because of the normal presence of calcium in natural water. As a result, this phenomenon has received quite some attention in the past. Kraeber and Boppel1 showed that quartz could be activated by calcium above pH 10 with sulfonate as collector. The feasibility of selectively separating quartz from hematite with calcium activation at relatively high pH was demonstrated by Clemmer, Clemmons, Rampacek, Williams, and stacy.2 Cooke and Digre3 showed with a bubble pick-up method that the minimum quantity of calcium ion required as activator for complete pick-up of particles occurs at pH 11.5 for an addition of 20 mg per liter sodium oleate. They also showed that larger additions of calcium (10-fold increase per unit decrease of pH) must be added for complete bubble pick-up as the pH is reduced. Schuhmann and Prakash,4 using a vacuum flotation technique, found that quartz could be floated with moderate additions of calcium chloride and oleic acid at neutral pH, providing the metal ion was present in stoichiometric excess over the quantity needed to form the normal soap with oleic acid. They also reported that calcium will function as an activator only in basic media. More recently, Eigeles and volova5 have shown that essentially complete flotation of quartz is obtained with 6 x 10-4 mole per liter calcium chloride and 1.7 x 10-5 mole per liter sodium oleate at pH 11.6. while no flotation is obtained at about pH 10.9 and below. The importance of adsorption of activator and collector at the air-liquid interface is also demonstrated in these systems. The important role that metal ion hydrolysis assumes in quartz activation systems was also demonstrated recently.6-8 A detailed investigation of metal activation in sulfonate flotation of quartz was undertaken in one system7 and yielded a number of interesting and important observations. Quantification of the data of this system7 to the extent desired was not possible, though, because certain species could neither be ignored nor accounted for accurately. These difficulties can be circumvented when calcium is involved as activator. This detailed analysis was undertaken to obtain a more quantitative explanation of calcium and metal ion activation in quartz flotation. EXPERIMENTAL MATERIALS AND METHODS Sodium alkyl aryl sulfonate9 mol wt 450, and pure potassium oleate were used as collectors. All other reagents used were reagent grade in quality, i.e., n-amyl alcohol as frother, KOH for pH adjustment, and calcium chloride. Conductivity water, made by passing distilled water through an ion exchange column, was used in the investigation. Quartz was prepared by leaching the sized sample (48 x 150 mesh) with HC1 until no iron could be detected in the leach liquor. The experimental equipment and procedure were the same as that described previously.6,10 EXPERIMENTAL RESULTS As the presence of precipitates was noted in all of the systems to which ca++ and collector were added, experiments were undertaken to determine the solubility products of calcium sulfonate and calcium oleate using a nephelometer. With this technique, collector is titrated into a known solution, which in this case was 5 x 10-5 mole per liter CaCl2 at pH 5.5. Upon precipitation of the calcium-col lector salt, e.g., calcium oleate, light is scattered and detected

Jan 1, 1967

By T. K. Perkins, L. R. Kern

A study of fluid mechanics, rupture of brittle materials and the theory of elastic deformation of rocks shows that, for a given formation, crack width is essentially controlled by fluid pressure drop in the fracture. Operating conditions which cause high pressure drop along the crack (such as high injection rate and viscous fluids) will result in relatively wide cracks. Conversely, operating conditions which cause low pressure drop (low injection rates and thin fluids) will result in relatively narrow cracks. Charts and equations have been derived which permit the estimation of fracture widths for a variety of flow conditions and for both horizontal and vertical fractures. INTRODUCTION There has been considerable speculation concerning the geometry of hydraulically created fractures in the earth&apos;s crust. One of the questions of practical importance is the width of fractures under dynamic conditions, i.e., while the fracture is being created and extended. Such width information could be used, for instance, to help estimate the area of a fracture generated under various conditions. Also, there has been a recent trend toward the use of large propping partiles.13, 15 Therefore is is desirable to know what factors can be varied in order to assure entry of the large particles into the fracture. There has been some work on fracture widths reported in the literature. In particular, there have been several Russian publications dealing with this sub-jeCt.1.31,3 These papers have dealt principally with the elastic theory and the application of this theory to hydraulic fractures. These studies have not led to an engineering method for estimating fracture widths under dynamic conditions. A recent paper3 has reviewed and summarized the Russian concepts. An earlier paper- from our laboratories also discussed the application of the elastic theory to hydraulic fractures. This first approach, based largely on photoelastic studies, has proved to be too simplified to accurately describe the fracturing process. However, these early thoughts have served as a guide during the development of more exact concepts. We would like to present in this paper our current concepts regarding fracture widths and some estimates of hydraulic fracture widths for several conditions. We believe that it is now possible to predict with fair accuracy the factors influencing fracture widths. Furthermore, the method of prediction has been reduced to a simple and convenient graphical or numerical calculation. CRACKS IN A BRITTLE, ELASTIC MATERIAL Many investigators2, 4, 30 have shown that competent rocks behave elastically over some range of stresses. Of course, if the tensile stress imposed upon a rock exceeds some limiting value, then the rock will fail in tension. In similar manner, there are some limiting shear stresses that can be imposed upon rocks. Hubbert and Willis11 have discussed the shear conditions which will lead to failure. Under moderate stress conditions (such as those likely to be encountered when hydraulically fracturing) and when stresses are rapidly applied, relatively, most rocks will fail in a brittle manner. Hence, for this discussion of hydraulic fractures in the earth&apos;s crust, we assume the rocks behave as brittle, elastic materials. Let us develop the discussion in the following way. (The following thoughts are applicable only to brittle materials.) 1. First we consider a brittle, elastic system. An energy balance will show the minimum pressure necessary to fracture rock, and from this pressure we calculate the minimum crack width resulting from extension of a hydraulic fracture. 2. Then we will show that, under ordinary fracturing conditions, fracture widths are appreciably greater than the minimum widths of extending fractures. In fact, we will find that crack width is controlled by fluid pressure drop in the fracture. 3. We will discuss pressure drops in fractures and resulting crack widths for various operating conditions and both vertical and horizontal fractures. 4. Finally, we will discuss the significance of these concepts, their relationship to fracturing pressures, etc. First, consider minimum fracture extension pressures. We can shed some light on this question by considering the theory proposed by Griffith7, 8 Yo explain the rupture of brittle, elastic materials. Griffith recognized that solid materials exhibit a surface energy8 (similar to surface tension in a liquid). The fundamental concept of the Griffith theory is that, when cracks spread without the application of external work (in the interior of an elastic medium which is stressed

By M. Cohen, D. Caplan

The scaling characteristics of three Fe-Cr alloys have been investigated by determining their weight gain vs. time curves at 1600° to 2000° F. The scales formed thereby have been examined using the techniques of X-ray diffraction and spectrographic and metal-lographic analyses in an attempt to explain the discontinuities in the curves and to elucidate the mechanism of scaling. DESPITE the considerable number of investigations that have been carried out on heat resistant alloys, the characteristics of the scales formed at high temperatures are not fully known. The research reported here was undertaken in an attempt to ascertain the mechanism of scaling of the stainless steels. Scaling experiments were carried out first, the weight increase of the specimens being followed continuously with time. It was observed that, as well as showing the expected decrease in oxidation rate with time, the oxidation curves showed breaks corresponding to intermediate periods of accelerated oxidation, after which protectiveness again increased. This phenomenon was observed with austenitic stainless steels (types 302, 309, and 330) and with Fe-Cr alloys (types 410, 430, and 446), but only the latter are treated in this report. An examination of the scales was made using the techniques of X-ray diffraction and spectrographic and metallographic analyses in an attempt to obtain a correlation between the nature of the scales and the oxidation curves. A search through the literature revealed only a very few previous reports of such periods of accelerated oxidation. Dunn&apos; found breaks in the oxidation-time curves of some Cu-Si alloys but saw no rational explanation of the phenomenon. Heindlhofer and Larsen2 attributed a discontinuity in the weight gain-time curve of iron at 1290°F to the formation of blisters, the subsequent cracking of which exposed an unprotected surface and permitted rapid oxidation until a new protective scale had been reestablished. They advanced no explanation, however, for what they termed the peculiar behavior of a 27 pct Fe-Cr alloy at 2000°F which gained weight very rapidly in between two periods of very slow weight gain. Portevin, Pretet, and Jolivet3 in describing breaks in the weight gain-time curves of Fe-A1 alloys suggested that they might be associated with the occurrence of localized and deeply oxidized areas on the specimens. Bandel4 in a general discussion of oxidation curves of heat resistant alloys considered that the discontinuities were due to a local disruption of the protective layer by the growth of iron-rich oxides. Day and Smith" in their report on the scaling of a large number of iron alloys noted but did not explain occasional relatively rapid changes in oxidation rate at higher temperatures. Chevenard and Wache6 found breaks, often two per specimen, in the oxidation curves of an 18-8 type alloy. They suggested that the cause might be a depletion in chromium of the surface layer of metal due to its selective oxidation, the resultant high concentration of iron and nickel in the scale leading to a poorly protective scale. McCullough, Fontana, and Beck&apos; explained the breaks in the oxidation curves of types 304, 430, and 410 alloys as due to mechanical ruptures. Experimental Work Table I lists the chemical compositions of the materials used. Cylindrical specimens 1/4 in. in diam and 11/2 in. long were machined from cold rolled % in. rod. After a fine finish cut with a sharp tool, the specimens were abraded while still mounted on the lathe with Nos. 2, 1, 0, and 00 metallographic grade emery papers. A 3/64 in. hole was drilled at a distance of 1/8 in. from one end to permit suspension in the furnace. Specimen Nos. 1, 2, and 3 were tested with this surface preparation. All others, after being similarly prepared, were electropolished in a perchloric-acetic electrolyte, electrical contact being made by pressing a tapered platinum hook into the drilled hole. The specimens were then washed in hot water, rinsed with distilled water, rinsed with methanol, dried at 120°F, and weighed. Thereafter,

Jan 1, 1953

By Shozo Saito, P. A. Beck

Mettrllographic and X-ray diffraction study of Cb-Co alloys in the Composition range of 7 to 33 nt. pct Cb, after annealing at 1175 °&apos;, showed that near 25 al. pct Cb on MgNi,-lype hexagonal Laves Phaseexists in a narrow composition range, and that an MgCl- type cubic Laves Phase occurs between approximately 27 and 32.6 ut. pd Cb. Lattice parameter and density measures indicated that, in both phases. the deviations from proper Loves sloichimetry result from the substitution of cobalt atoms for some 0f the columbium atoms. Tlle same phases occurant 1000&apos;C, together with an additional phase of unknown structure, which appears between the hexagonal Laves phase and the cobalt-bose terminal solid solutions KOSTER and Schmid&apos; identified a phase corresponding to the composition VCo,, and more recently the crystal structure of this phase has been determined.&apos; In the Ta-Co system Korchynsky and Fountain recently found two intermediate phases at the composition Taco,, one of them metastable. In contrast to the V-Co and the Ta-Co systems, in the Cb-Co system no intermediate phase has been found4 at the composition CbCo,. The present investigation was undertaken in order to reexamine the question of the existence of such a phase. EXPERIMENTAL PROCEDURE Twelve alloys were prepared by arc-melting in a water-cooled copper crucible under helium atmosphere. Electrolytic cobalt and 99.9 pct pure colum-bium powder have been used as starting materials. It was found that melting losses can be reduced by compressing the colunlbium powder in the form of thin pellets before melting. For the alloys used the melting losses were not higher than 1 pct. The intended compositions of all alloys and the chemical analyses of three of them are given in Table I. Specimens from all alloys were annealed in evac- uated fused silica tubes at 1175°C for 3 days and quenched in cold water. A second set of specimens of most alloys was annealed at 1000°C for 7 days and then quenched in cold water. The annealed and quenched specimens were examined metallographically, using the following etchant: 60 pct glycerine +20 pct H,NO, + 10 pct HF + 10 pct water. Powder specimens for X-ray diffraction were prepared by crushing annealed solid specimens in a mortar. Alloys containing 27.3, 28, 29.7, and 32.6 at. pct Cb annealed at either 1175" or 1000°C were very brittle and it was found unnecessary to reanneal the powders. However, alloys containing 24.8 at. pct Cb, or less, especially those annealed at 1000°C, were much less brittle and re-annealing was required to remove the strains present in the crushed powders. In each case reannealing was done at the same temperature at which the corresponding solid specimens were annealed and it, too, was followed by quenching in cold water. In many instances X-ray diffraction patterns were also taken of the polished and etched solid specimens and compared with the corresponding X-ray diffraction patterns obtained with powders. The X-ray diffraction patterns were taken with an asymmetrical focusing camera, using CrK radiation. For precision lattice parameter measurements some X-ray diffraction patterns were taken with a symmetrical focusing camera, again using CrK radiation. EXPERIMENTAL RESULTS A microscopic examination of the alloys annealed at 1175°C revealed that the alloy containing 25.5 at. pct Cb was composed of a single phase, but that the 24.8 at. pct Cb alloy did contain a small amount of a second phase, identified by means of X-ray diffraction as having a fcc structure, undoubtedly the terminal solid solution based on cobalt. Apart from the few very weak lines corresponding to this minor phase, the X-ray diffraction patterns of these alloys could be well interpreted in terms of a MgNi,-type hexagonal Laves phase structure. The indexing of the X-ray diffraction pattern, Table 11, yas based on the lattice parameter values a, = 4.740A and c,

Jan 1, 1961

By P. S. Kotva

Dislocation substructures in superalloy matrices of varyzng co)npositions have been studied. In general, it has been found that the alloys can be classified into &apos;&apos;high", &apos;&apos;medium", and "low" stacking fault energy classes based on the type of dislocation substructure observed in the matrix and that the substructure can be correlated to the stacking fault energy. The effect of different types of dislocation substructure and dislocation reactions on the intragranulur precipitation of carbide phases has been studied. In a Ni-Cv-Mo-Fe matrix, precipitation of MC carbides in association with stacking faults has been observed. In most superalloys, solid-solution strengthening and precipitation hardening are the chief mechanisms employed to achieve strength. The latter contribution to strength is usually achieved by the precipitation of / in certain wrought alloys. Insufficient attention has been given to the problem of obtaining strength in su-peralloys by controlling precipitation of carbides on imperfections within the matrix. The present work was undertaken to investigate the dislocation substructure in various superalloy matrices, to study the effect of such substructure on subsequent precipitation of carbides in the matrix, and to investigate whether certain modes of precipitation of carbide phases found in austenitic stainless steels2"4&apos;6 would occur in nickel-base alloy matrices with dislocation substructures of the same type as those found in austenitic steels. 1) EXPERIMENTAL TECHNIQUES Five-pound heats of the various alloy compositions reported here were vacuum-cast. The ingots were given light deformation by rolling to break up the as-cast structure and then homogenized for 24 hr. HASTELLOY alloy X (nominal composition: Ni-2OCr-17Fe-8Mo-0.05C) was homogenized at 2150°F and In-cone1 625 (nominal composition: Ni-20Cr-5Fe-8Mo-3.5Cb-0.05C) was homogenized at 2280°F. Fabrication of 0.004-in. sheet was achieved by cold rolling with intermediate annealing treatments being carried out at the same temperature as those used for homogeniza-tion. Each solution anneal was followed by quenching. The aim of this procedure was to redissolve as much of the primary carbide phase as possible. Samples of the 0.004-in. sheet were cut and encapsulated in quartz capsules and then heat-treated in the tube furnaces. Thin foils were prepared using an ethanol-10 pct perchloric acid bath at 32°F and at a voltage of 22 v. A "window" technique was employed. Observations were made on a JEM-7 electron microscope operating at 100 kv. 2) EXPERIMENTAL RESULTS a) Types of Dislocation Substructure. Fig. 1 shows a schematic correlation between stacking fault energy, SFE, and the type of dislocation substructure observed in various matrices of nickel- and cobalt-base alloys. A precise quantitative determination of stacking fault energy is not implied in the figure but the correlation between stacking fault energy and the type of dislocation substructure obtained allows alloys to be divided into three classes in analogy with the classification employed by Swann and ~uttin~&apos; for binary alloys of copper. Class I alloys are associated with a "high" SFE and show a cellular substructure of dislocations as typified by the micrograph of a thin foil of pure nickel deformed 4 pct at room temperature in Fig. 2. With decreasing SFE the tendency toward cell formation is lessened and dislocations tend to be arranged in coplanar groupings. Examples of this class of alloys with "medium" SFE are provided by the mi-crostructure of solution-heat-treated, quenched, and deformed thin foils of HASTELLOY alloy X, "Waspaloy" (prior to any aging), and Inconel 625. Fig. 3 shows a thin-foil micrograph of an alloy of Inconel 625 composition, solution-heat-treated, quenched, and deformed 5 pct at room temperatures. No evidence of any cell structure can be obtained in materials of "medium" stacking fault energy, Fig. 3, even after severe deformation. The stacking fault energy of the alloy shown in Fig. 3 is, however, not low enough to make the dissociation of dislocations visually obvious. As stacking fault energy decreases further, with successive addition of solute in the matrix, there is an increased tendency toward dissociation of dislocations and cross slip becomes progressively more difficult. Eventually, when the stacking fault energy is "low" enough, complete dissociation of dislocations is seen to occur as shown in Figs.

Jan 1, 1969

By R. Stickler, A. Vinckier

An optical and electron microscope study was made on a commercial 302 stainless steel heat treated for massive carbide precipitation. Convincirg evidence was obtained that the grain boundary precipitate does not grow away from the grain boundary into the matrix, but grows as a network of large thin dendrites in between the grains. IN austenitic stainless steels the carbon in supersaturated solution precipitates when the steel is heated in the temperature range 450" to 1000°C. During such heat treatments the chromium-rich carbide occurs primarily at the grain boundaries and has adverse effects on the corrosion resistance and low-temperature ductility of the material. It has been shown that the morphology of the precipitated particles differs widely depending on the time and temperature of the heat treatment, the nature of the boundary, the misfit between the grains, and so forth.1"5 It was assumed by Mahla et al.,&apos; Streicher,&apos; and Mc Nutt&apos; that the carbide particles which nucleate in the grain boundary grow in various geometric or dendritic forms away from the boundary into the matrix. However, Kinzel,&apos; Hatwell et a, and Plateau et aL4 found that the particles nucleate in the grain boundary and grow as a network of thin dendrites in the grain boundary interface. We have made a comprehensive studyg of the precipitation occurring in a commercial 302 austenitic stainless steel heat treated for times ranging from 0.15 to 1500 hr at various temperatures from 480" to 1065"~. This study was made to elucidate the influence of heat treatments on both the mechanical and the corrosion properties of this steel. Part of this investigation which is pertinent to the morphology of the grain boundary carbides referred to above is separately reported here. We found that the particles which nucleated in the boundaries grew in the interface of these boundaries, thus supporting the viewpoints of Kinzel,&apos; Hatwell et al.,3 and Plateau et al.4 Furthermore, when carbide particles nucleated in the matrix very close to the boundaries, they possessed a morphology distinctively different from the particles growing in the grain boundaries. MATERIAL A study of metallographic samples and of fracture surfaces of a 302 stainless steel is reported in this paper. The composition and heat treatments are listed in Table I. Polished and etched samples were examined und813r the optical microscope, and carbon extraction replicas of etched micrographic samples and various fracture surfaces3&apos;8&apos;9 were examined under the electron microscope. RESULTS AND DISCUSSION A representative optical micrograph of the 302 steel, condition A, is shown in Fig. l(a). Particles can be seen on the grain boundaries but no traces can be found of particles which grow from the grain boundaries into the matrix. A carbon extraction replica of this sample shows numerous large thin dendrites, Fig. l(b). The lateral dimension of such carbide particles vary up to 100 p, and their thickness estimated from the amoun! of electron penetration i:; between 500 and 1000A. Such large dendrites are extracted from almost all grain boundaries and, if they had grown into the grains, they would definitely be revealed by etching traces in the matrix, Fig. l(a). The reason why these large dendrites on the extraction replica appear to be grown into the grain is due to the mechanism of the extraction replica process. Thus, these dendrites are supported by the carbon replica film only at the edges originally along the grain boundary trace A-A, Fig. l(b), in the polished metal section and have subsequently fallen over onto the carbon replica film during handling. Although such dendrites generally fall only to one particular side of the grain boundary trace, one finds occasionally that parts of a dendrite have fallen to both sides, as shown in Fig. l(b). Further evidence for the growth of carbide in the grain boundary can be obtained from the appearance of fracture surfaces. A small impact specimen of the 302 steel, condition A, was broken at liquid nitrogen temperature. The fracture path follows the

Jan 1, 1962

By D. L. Sikarskie, B. Paul

A theory is presented for the static penetration of a single rigid wedge into brittle material. The material considered is one which exhibits both crushing and chipping phases in the penetration process. If the wedge angle and three parameters are specified, the theory predicts forces and associated penetrations during both the crushing and chipping phases. For certain ranges of the parameters agreement with the limited experimental data available is promising, except for the initial phase of the penetration process where refinements on the proposed theory are required. The theory also predicts that for certain values of the wedge angle and other known parameters, the chipping process does not occur and penetration is due entirely to crushing. When viewed in detail, the drilling of rock by percussive means involves, among other things, system dynamics, actuating forces, dynamic stress levels and the actual penetration mechanism of the bit into rock. If rock drills are to be significantly improved, a thorough understanding of the entire system would be highly desirable. In this paper, one aspect of the system, namely the mechanism of penetration of the bit, will be studied in detail. It has been found1 that for the velocities encountered in percussive drilling (of the order of 20 fps) a static analysis adequately describes the penetration process, at least for some rocks. Hence, we will only be concerned with describing analytically the static penetration of a single wedge shaped tool. It will further be assumed that the wedge is long enough to permit a two-dimensional analysis. Numerous authors have studied the static penetration of a wedge into rock. The following papers give some of this work and provide additional references to other work. Cheatham2,3 has assumed the rock to behave plastically and has obtained force-penetration equations for both Coulomb-Mohr and parabolic yield criteria. Evans and Murrell4 have studied the penetration of two types of coal and have found equations relating the penetration characteristic (P/dSc) to wedge angle for the various strength coals tested. race&apos; attempted to find a correlation between hardness as determined by indenting the material and other mechanical properties and concluded that the results of such a test are generally inconclusive. His paper however contains a very extensive bibliography on the indenting of many different materials. Gnirk6 also has a fairly complete literature review on the static penetration of rock, of which he makes use in his indexing studies. A wide range of behavior is found in the wedge penetration of different rocks under different external conditions. For example, a rock that is essentially elastic-brittle at standard pressure may become elastic-plastic at a high confining pressure.7 It has also been observed4. " that some rocks will merely be crushed and indented by a wedge, whereas others will crack and form chips, furthermore the existence or non-existence of chips depends in great measure on the geometry of the indentor, type of rock and the depth of penetration. Hence, to attempt a theory which embraces all possible behavior is not practical at present. We, therefore, confine our attention to predicting the force-penetration characteristic and volume removal behavior for a type of rock which exhibits both crushing and chipping phases in the penetration process. Such behavior is characteristic of the harder rocks such as granites and represents a more difficult problem than the behavior of softer rocks such as coal and certain sandstones. In this preliminary study an attempt will be made to describe only the essential features of this complex penetration process. A qualitative description of these essential features is obtained with the aid of Fig. 1.1, where a wedge of vertex angle 28 is shown at some intermediate stage of the penetration process. As the wedge advances, the rock is fragmented (i.e. crushed) in some local region surrounding the wedge, the shape of this region being unknown. Simultaneous with the fragmentation in this local region, essentially elastic stresses are assumed to be building up in the surrounding rock. When a certain penetration level, di+1, is reached, the stresses along some surface are sufficient to cause failure and a chip is thus formed. The process now repeats, i.e., a crushing phase followed by the formation of a chip.

Jan 1, 1965

By D. T. Camp, J. A. Clum

WITH experience, the indexing of back-reflection Laue patterns for cubic crystals is usually a straightforward matter. However, for noncubic systems where in general tables of interplanar angles are not available or when inexperienced personnel are involved, properly indexing a crystal is normally a tedious, time-consuming affair. The authors have written a digital-computer program which calculates and prints out a table of interplanar angles for an arbitrary crystal structure and then systematically searches through this table attempting to obtain a consistent fit to back-reflection Laue data supplied by the user. Of course it is possible simply to calculate a desired set of interplanar angles should this be the only requirement. The program was originally written in ALGOL for use on a Control Data G-21 computer and a preliminary version is described elsewhere.&apos; A version in FORTRAN TV which has been run on an IBM 7040 and one in FORTRAN II run on an IBM 1620 are also available. While it is not the purpose of this communication to describe the program in detail, an indication of how the program operates may help one to decide whether the program would be useful under particular circumstances. The hypothetical example chosen involves the indexing of the zinc crystal which has a hexagonal structure and a c/a ratio of 1.856. Input data for this example consists of only nine cards: The first card controls the list of families of planes to be considered. If the Miller indices of a prospective family are (h k 1), the first digit places a limit, in this case 3, on the absolute values of any individual index. The second digit limits the sum (h +k + l + 1), in this case to 5. Therefore the families (013) and (112) are considered but the family (122) is not. All systems, including the hexagonal, are treated using three-digit Miller indices. The second card contains the crystallographic parameters required to define the system. The first digit is 0 if the system is rectangular, that is all angles are 90 deg. If the system is nonrectangular, as in this example, the digit 1 so indicates. The next three values are the lengths of the sides of the reference cell, a, b, c. The final three entries on the card are the angles, a, 8, y between the sides. The digit 0 on the third card indicates that more data follows, the digit 6 shows that a set of six planes is to be indexed, and the value 2.0 indicates that agreement between a tabulated angle and an input angle is considered adequate if their absolute difference is less than 2 deg. The fourth card lists the measured input angles. a12 = 38 deg, a13 = 24 deg, and so forth. More input angles are listed on cards five to eight with the latter giving the input angle 058 = 40 deg. The final card in this series indicates by the digit 1 that no more data is to be processed. The program operates in the following manner: 1) The input data from cards 1 and 2 is read, thereby indicating the crystal system to be examined and the crystallographic parameters of the particular crystal to be indexed. 2) A table of interplanar angles is generated. 3) The input angles contained on cards 4 to 8 are read. 4) The measured input data is systematically compared with the generated table of standard angles. All combinations of poles whose interplanar angles compare with the requisite, specified accuracy are printed out. If no adequate fit is found an indication of this is printed. A typical line from the generated table of interplanar angles is: (001) - (111) 74.92 64.99 It can be shown that in the Miller-Bravais system the first value corresponds to the angles between (0001)-(1121) and the second to that between (0001)-(1011). This particular set of data gave the following result for the planes 1 to 6: (011) (110) (121) (111) (112) (010) The ALGOL version also has the option of simply providing the Greninger-chart coordinates ? and 6

Jan 1, 1967

By Frank Doxey

AT Dominion Steel & Coal Corp. it has long been recognized that continued mechanization of mine operations is necessary in the Pictou, Cumberland, and Sidney coal fields of Nova Scotia. The varied physical conditions in these fields call for special consideration of individual cases before planning is finalized. Because standard equipment cannot be procured which would operate successfully, many experiments have been necessary over the years to keep pace with the progress made in other countries. There are two mines, producing 2000 tpd, located in the Pictou coal field. The field is badly distorted and crossed by many faults. Seams are highly inclined and irregular and vary in thickness from 5 to 40 ft. Entries are difficult to maintain because of squeezing of the coal. ribs and movement of the roof and pavement. Output from the three operating mines in the Cumberland field is 3000 tpd. The field is highly inclined, inclination varying from 12° to 32°. Overlying beds consist of shales and massive sandstone lenses of extreme toughness and are responsible for bumps when the stresses are relieved by extraction. At greatest depth these are among the deepest coal workings in the world. Depth of cover ranges from 2300 to 4000 ft. This prohibits room-and-pillar working and necessitates longwall operation. Working of contiguous seams concurrently to maintain output increases the already difficult conditions. The Sydney field, with a frontage of about 30 miles, is the most important of the Nova Scotia coal fields. With the exception of one small area it is now wholly submarine. Output is approximately 21,000 tpd. Seams are 21/2 to 8 ft thick, and cover in the areas varies from 600 to 2300 ft, with an average of 1500 ft from sea bottom to the top of the seam. The seams dip in a seaward direction, pitches ranging from 6" to 4.0". The shoreline is the last place of entry to the seams and distance from the bank to the working faces is generally over 3½ miles, in some cases as much as 6½ miles. Ventilation is a problem and requires the construction of large permanent airways. Getting and Loading Coal: In 1925, in view of heavy pressures exerted by thickness of cover overlying the seams, roadways and pillars of the room-and-pillar system being worked began to break up and coal was lost. It was decided that a change in the method of extraction in areas with heavy cover was necessary, and experiments were made with many short walls and longwalls varying between 90 and 250 ft. Trial and error proved that the best operating length was between 400 and 500 ft, delivering all coal to the dip, with roadways to the face following a level course. The change-over was gradual, and the technique of roof control developed with the system, so that falls to the face are now very infrequent. An advantage of longwall mining is that it yields 95 pct extraction, especially important in coal seams of high quality or in seams where faults or disturbances restrict the workable areas. This percentage of extraction is based on the fact that the longwall advancing system takes development faces where pitch permits instead of driving headings and leaving roadway pillars. This system yields high tonnage during development and limits loss in extraction to duff left during operations. Accompanying disadvantages, on the other hand, are the heavy construction cost of main roadways and the necessity of driving all new flank face roadways through the gob. If the main roadways are driven through the solid, and large enough pillars are left on each side for protection against flank face weights, then the width of solid coal is approximately 1700 ft. This represents 10.6 pct of the coal available, or 89.4 pct extraction of the whole. These pillars, however, are of such size that they provide a useful pillar drawing area as a final operation of the mine. It may be that although the seam cannot be generally mined by the room-and-pillar method, it can be adapted to

Jan 1, 1955

By R. E. Reed-Hill, W. H. Hartt

The second order, {1011}-{1012} twin bands observed in critically deformed magnesium are often accompanied by an unusual form of kinking. These kinks, which lie adjacent to and run more or less parallel to the twin band habit, allow plastic deformation that occurs inside the twins to be accommodated into the matrix. The bend planes of these kinks cannot be explained using slip dislocations with Burgers vectors lying in the basal plane. A mechanism involving a single set of {1012)(1011) dislocations is proposed to account for the kink band habit, in good agreement with the experimental observations. It has been shown that second order, {101l)-{1012} twinning is an important phenomenon for magnesium deformed in the ambient temperature range. A detailed study of these twins has recently led to a better understanding of their irrational habit plane1 and their relation to fracture in magnesium.&apos; This paper is concerned with a third aspect of these twins; this being the kink bands, originally referred to as shear accommodation kinks,3&apos;4 that are often induced in the adjacent matrix. A twin band and its shear accommodation kink usually appear as a single macroscopic deformation, as seen in Fig. 1. The complex nature of these deformed regions is easily revealed, however, with the aid of a suitable microscope. It has been proposed374 that the primary function of these kinks is to accommodate the nonhomogeneous deformation that normally occurs in the second order twins. The twins tend to form as small discrete lamellae lined up approximately one in front of the other.&apos;&apos;&apos; Very large plastic deformations varying in magnitude from one twin to the next, may occur inside these lamellae. The kinks serve both to pass this strain into the matrix and to accommodate strain variations between twins. Deformation within the kinks, subsequent to their formation, has also been observed;3,4 and it is thought that this contributes to the strain accommodation process. The bend planes of the kinks have a habit near that of the twin band itself, which lies about 56 deg from the matrix basal plane. This orientation does not bisect the angle formed between the basal plane to either side of the bend plane and therefore differs markedly from the kink structure usually observed in hcp metals.&apos;-&apos; The present paper reports the results of a study of shear accommodation kinks and proposes a possible solution to the problem of the orientation of the bend plane. EXPERIMENTAL PROCEDURE Rectangular cross-section tensile specimens with axes parallel to (1010) and faces to (1210) and (0001) were cut and acid machined from a high-purity magnesium single crystal. After straining on an Instron machine the specimens were examined by both optical and replica electron microscopy. The basic procedures have been previously reported."&apos; EXPERIMENTAL RESULTS AND DISCUSSION Structure of Shear Accommodation Kinks. A typical, large (101l)-{1012) twin band with its associated shear accommodation kink is shown running diagonally from upper left to lower right in Fig. 1. In this optical micrograph the twin band, consisting of a row of small, highly deformed twin lamellae, is visible as a narrow dark band along the left hand edge of the structure in question. The kink lies to the right of the twins, is approximately three times as wide, and is lighter in contrast. The horizontal slip lines visible on the general specimen surface correspond to matrix basal slip and are parallel to the tensile axis. Note that on the right-hand side of the band these slip lines can be followed from the matrix into the kink. At the kink band boundary the slip lines suffer a clockwise rotation of about 25 deg. Rotations of this magnitude are not uncommon. When a surface such as that in Fig. 1 is given an etch1 making it sensitive to polarized light, it has been observed that the slip traces in the kink are parallel to the basal plane trace in this region. This is in excellent agreement with the assumption that these regions are indeed kinks. Fig. 2 is an electron micrograph of this same twin band and kink. Note that a row of small supplimation pits has formed

Jan 1, 1969

By Z. Moser, W. Ptak

The experiments were carried out by the method of measuring the electromotive force of concentration cells having zinc as a reference electrode, the second electrode being the liquid alloy Zn-Sn-Cd-Pb. The electrolyte consisted of liquid chlorides and had zinc ions. The measurements were made for seventy -five alloys of different mole fractions within the temperature range of 714° to 877°K. The experimental results enabled the calculation of the activity of zinc in tested solutions. The activities of zinc were calculated by means of Krupkowski&apos;s formulas.3 In addition, the formulas for coefficients of activity of zinc, tin, cadmium. and lead as the function of composition and temperature were given. Activity of zinc was compared with the values obtained from experimental results, and good agreement has been observed. On this basis it can be stated that the theoretical formulas are suitable for determining the thermodynamic properties of liquid quaternary metal solutions. IN the metallurgical processes being carried out at present multicomponent liquid metal solutions take part. For the thermodynamic analysis of these processes it is necessary to know the thermodynamic properties of these solutions. Therefore, many experimental and theoretical papers deal with this problem. The theoretical papers are generally based on the assumption that the structure of liquid metals is similar to their structure in the solid state. In this manner the model of liquid solution, consequently described by means of statistical thermodynamics, has been accepted. This method is being lately developed, especially for solid solutions. Statistical thermodynamics was applied among others by Guggenheim 1 for describing the thermodynamic properties. Unfortunately, the formulas of statistical thermodynamics are often not suitable for the interpretation of experimental results. Attention should be drawn to the relations obtained by means of formulas of phenomenological thermodynamics which always have constants derived with the aid of experimental methods. In the case of the multi-component solutions which contain some additions of impurities besides the basic metal, wagner2 introduced interaction parameters. Equations for the relationship between the activity coefficients and composition were also given by Krupkowski." he application of these formulas requires a good knowledge of the thermodynamic properties of the corresponding binary systems. In these formulas, as in Wagner&apos;s, there appear constants which should be determined from ex- perimental data. Nowadays, different experimental methods are applied for evaluating the thermodynamic functions of solutions, for instance: vapor pressure measurements, calorimetric methods, and the measurements of electromotive force of concentration cells. In the present paper this last method for evaluating the thermodynamic properties of four-component systems, Zn-Sn-Cd-Pb, was applied. For instance in the case of Zn-Sn solutions Alabyshev and Landratov, 4 Fiorani and Valenti, 5 and ptak6 performed the investigations. The Zn-Pb system was worked out by Kleppa 7 and Cd-Pb and Cd-Sn by Elliot and chipman.&apos; This method was also applied for determining the activity of zinc in ternary solutions. 1) EXPERIMENTAL METHOD The experimental arrangement with detailed description is given in Fig. 1. It consists of resistance furnaces, one serving for melting samples and the other containing the flat-bottomed, measuring quartz tube with the liquid electrolyte. Liquid metals and alloys are in glass supremax tubes, which have an opening in their lower part above the metal level. This opening allows the filling of the tubes by the electrolyte. In these tubes tungsten wires are placed which by means of suitable conductors are connected with a potentiometer. It is assumed that tungsten dissolves Fig. 1—Schematic diagram of the experimental arrangement for the investigation of the thermodynamic properties of liquid metal solutions: 1, resistance furnaces; 2, autotransfor-mers; 3, galvanometers; 4, regulator of temperature; 5, gas purifier with concentrated H2SOP; 6, U-tube with P2O5; 7, thermostats; 8, steel block for thermostating; 9, supremax tubes for alloys; 10, tungsten electrodes; 11, inlet and outlet of argon; 12, measuring quartz tube; 13, tube for melting samples; 14, tube for thermocouple; 15, cover of quartz tube; 16, rubber seal; 17, bottom cover; 18, outlet of electrodes to potentiometer; 19, outlet of thermocouples to potentiometer; 20, upper view of the quartz tube cover; 21, orifices for cover screws; 22, orifice for argon inlet; 23, orifice for thermocouple; 24, orifices for tubes containing liquid metals; 25, inlet for water-cooling system.

Jan 1, 1969

By R. Taggart, D. H. Polonis, W. C. Gallaugher

In the Ti-Cu system, the a&apos; phase can be produced over a wide range of alloy composition witJwut the retention of measurable amounts of the ß or ? phases. This paper reports on the decomposition of this hexagonal martensite phase front the standpoint of solute corzcentratiorz, tempering temperature, and coherency strain condition. The mechanism of precipitation during tempering comprises localized precipitation which is followed by discontinuous precipitation if sufficient coherency strains are present. The localized precipitation process in hypoeutectoid alloys is described by the generalized Johnson-hiehl equation and an activation energy of 46,000 cal per mole. In hypereutectoid alloys the corresponcEing activation energy is 51,000 cal per mole. The rate-controlling process has been proposed as the difision of copper along a&apos; platelet interfnces. SEVERAL investigations have been reported concerning the kinetics of decomposition of the mar-tensitic a&apos; phase in titanium binary alloys.&apos; In the Ti-Mo system,&apos; two modes of a&apos; decomposition have been observed in the presence of /3 phase; one of these involves the precipitation of fine a from a&apos;, and the other involves diffusion across the a&apos;-ß interface. In studies of the Ti-Cr system, Rostoker2 did not detect the formation of TiCr2 during tempering. In Ti-Ni alloys,3 the intermediate phase Ti2Ni has been found to precipitate directly from a&apos; along the interfaces between plates. With the exception of the study of Ti-Ni alloys the previous investigations of tempering phenomena in substitutional martensites are mainly qualitative and do not present a detailed description of the precipitation processes. The following limitations restrict the correlation of the microstruc-tural processes and reaction kinetics during tempering in most binary-alloy systems. 1) A mixture of at least two phases characterizes the constitution of quenched alloys. 2) Difficulties have been encountered in obtaining uniform structures throughout quenched samples. 3) The reaction products, and in particular their morphology. have not been clearly resolved. 4) The martensitic a&apos; phase forms over only a limited composition range for most titanium-base binary alloys. Gomez and polonis4 showed that the Ti-Cu system provides an excellent basis for investigating the tempering of a&apos; over a range of composition without the complication of retained P or the transition w phase. In the present work the effects of solute concentration, tempering temperature, and coherency strain conditions are considered with reference to the over-all precipitation process in quenched alloys of the Ti-Cu system. Both microstructural observations and kinetic data are correlated to define the rate-controlling processes which govern the observed localized and discontinuous precipitation reactions. An earlier paper5 was devoted to a discussion of the modes of heterogeneous nucleation of Ti2Cu from the martensitic a&apos; structure. The present paper will therefore emphasize the progress of the tempering reaction beyond the initial stages. EXPERIMENTAL METHODS The Ti-Cu alloys for this study were prepared by conventional arc-melting procedures. Chemical analysis revealed that the alloy buttons contained approximately 0.02 wt pct 0, 0.04 wt pct N, and within 0.1 wt pct of the intended copper concentration. The progress of the tempering reaction was followed by means of electrical-resistance measurements utilizing a Kelvin double bridge, microhard-ness readings with a 400-g load, and X-ray dif-fractometry patterns to reveal line-broadening effects. Metallographic specimens examined at magnifications greater than X1000 were shadowed with germanium to reveal fine structural details. Direct carbon replicas were prepared for the electron-microscopy studies. EXPERIMENTAL RESULTS Property Changes. The changes of microhardness that accompany the precipitation of Ti2Cu from a&apos; are shown in Figs. 1 and 2. As the solute concentration increases the peak hardness, for a given tempering temperature, increases. In alloys of given composition the time to reach the peak hardness agreed with the time to attain maximum X-ray diffraction peak breadth, as shown in Fig. 3. The maximum hardness and the maximum line breadth increased with lower tempering temperatures, and the time to reach the maximum also increased. The a&apos; peaks broadened during the initial stages of tem-

Jan 1, 1965

By Arnulf Muan, Hobart M. Kraner

Ferromanganese alloys react with aluminu-silica brick in blast furnace hearths and cause the formation of new phases with low refractoriness and consequent failure of the refractory lining. The nature of these reactions is explained on the basis of petrographic observations, thermodynamic data, and Phase equilibrium considerations. Animproued hearth design resulted from these findings. The production of ferromanganese in blast furnaces presents many problems which are not encountered in the production of iron in the same furnaces. One of the most serious of these problems is the rapid failure of refractories caused by their reaction with the ferromanganese metal. The present paper describes such a "hearth attack", its symptoms, causes, and cure. Following an introductory discussion of operating practice in ferromanganese blast furnaces, results are presented of a petrographic examination of samples from a furnace which had to be shut down because of refractory failure. The causes of this failure are then analyzed on the basis of petrographic observations combined with thermodynamic and phase equilibrium data available in the literature. The latter type of data were subsequently used as a guide in recommending improvements in hearth designs which have since proven themselves successful in practical operations. I) FERROMANGANESE BLAST FURNACE PRACTICE It is considered good practice to blow in a furnace on iron and operate it in this way for a period of time preliminary to producing ferrornanganese. During this time, iron generally penetrates the bottom refractories six or more feet below the original working surface of the hearth. Not only does this metal pervade the joints to these depths, but the pores of the refractories are usually also filled by molten iron. The high throughput of the iron furnace provides ample heat to maintain a high temperature in the hearth refractories. This, together with a high ferrostatic pressure, causes porous clay brick of the hearth to shrink. During subsequent use of such a furnace in ferromanganese production, the iron in the pores of hearth brick if; replaced to some extent by ferromanganese. The replacement is usually not complete. This is probably due to the lower metal throughput and lower prevailing temperatures resulting from this in the brick of the hearth bottom. When the ferrornanganese furnace is banked—or when the temperature in the furnace falls due to a furnace delay—-manganese oxidizes even though the atmosphere is largely CO. Considerable expansion accompanies this oxidation of manganese from metal to oxide. The hearth refractories are then subjected to the disintegrating forces of the volume expansion. These forces may in extreme cases be large enough to lift the furnace off its mantle supports as was described in a previous paper.&apos; When cooling takes place slowly, however, and the temperature remains at a fairly high level, the refractories undergo fluxing action by the MnO. This latter reaction and the reduction of SiO2 of the clay brick is the general subject of the present paper. The observations to be described herein were made on a ferromanganese furnace located at the Johnstown plant of Bethlehem Steel Co. The furnace was lined entirely with clay refractories and had operated on iron for 266 days and on ferromanganese for 96 days prior to being taken off because of a hearth wall failure. II) PETROGRAPHIC EXAMINATION AND CHEMICAL ANALYSIS The photograph reproduced in Fig. 1 shws a cross section of the upper part of an 18 by 9 by 4-1/2 in. bottom block removed from the blast furnace. This brick came from a depth of approximately 6 ft below the original working face of the bottom. It will be noted that the 4-1/2 in. dimension is almost the same as when the brick entered the furnace. Three characteristically different zones marked I, II, and III on the print of Fig. 1 are apparent. Results of chemical analyses of the original brick and samples from each of these zones are listed in Table I. Petrographically the various zones were characterized as follows: The central zone marked I was essentially un-reacted brick. The microstructure consisted of fine needles of mullite, and the pores in this entire area were filled with iron. This is characteristic of

Jan 1, 1962

By L. Larson

SMELTERMEN in the copper industry know that punching the tuyeres of a copper converter is a difficult, disagreeable, and at times a hazardous job. Knowing this, many men in the industry have given serious consideration to punching by mechanical means. As evidence of such consideration, a great many patents have been issued covering various mechanical devices or machines for doing this task. In 1942, as war-created manpower shortages became more acute, it became increasingly difficult to get men to punch tuyeres. Faced with this situation at the McGill smelter, it was decided that an all-out effort should be made to develop some sort of a mechanical punching device. The various patents were studied over thoroughly but none of the devices seemed suitable, all were discarded and it was decided to develop one, using the ideas of the personnel at McGill. Initial test work indicated that a separate punching device should be attached to each tuyere. This meant that an adapter would have to be developed which would accommodate such a device; the adapter to be so constructed that it could be substituted for the regular Dyblie valve head, and be punched either by mechanical means or by hand. Also a method for quickly attaching or detaching the punching unit would have to be devised. If the punching unit was attached to the adapter, then the punch rod and tip would have to remain inside of and reciprocate within the tuyere pipe. This last requirement meant that the punching device, the adapter, the piston rod, and punch rod must be in perfect alignment. The whole arrangement thus would become an integral part of the converter and would rotate along with the tuyere line to all the positions required for converter operation. If the puncher was to rotate with the converter, there was also a problem of limited clearance. The construction of a device to meet all of these conditions imposed many problems. In the latter part of 1942, two pieces of equipment were constructed and tried out under test-stand conditions. Both of these devices were very crude, but test-stand operation indicated that progress was being made. Neither of the units was considered good enough to be attached to and tried out on a tuyere of an operating converter. In May 1943, work was started on another device and in August of that year it was attached to and actually punched a single tuyere of a converter on an experimental basis (fig. 1). This unit was essentially a cylinder 3 in. in diam and about 15 in. long inside. Valve ports were so located as to provide a 1-in. cushion on each end of the stroke. The cylinder ports were piped to a 3/4-in. four-way disk valve. High pressure air (90 psi) was delivered to the valve by means of a long hose, thus making it possible to supply air to the device at all operating positions of the converter. The forward and return punching strokes were accomplished by shifting the valve handle as required. With the 3/4-in. valve, stroke velocities from 15 to 18 fps were achieved. Punching with this experimental arrangement was carried on for some time, but many difficulties were encountered. The punch rod tips often stuck in the tuyere accretion, indicating that more energy of some sort was necessary to avoid sticking the punch rod. To overcome sticking, experiments continued with a speeded up unit and although progress was made, troubles of various kinds continued to appear. On this unit, piston cup seals passed the valve ports which proved to be of very poor construction. Also the piston, driven forward at approximately 28 fps, would often bottom metal to metal in the forward end of the cylinder causing both mechanical and operational trouble. Sometimes the punch rod and at other times the piston rod would break loose and be shot through the tuyere pipe into the converter. Bottoming and poor timing of valve reversal caused a bounce and a hesitation at the end of the forward stroke, with the result that the punch rod

Jan 1, 1951

By T. Yamasaki, S. Usu

Adsorption of potassium dodecyl xanthate from aqueous solutions on artificial and natural zinc sul-fides was studied by means of infrared absorption spectroscopy. The adsorption species and their stabilities varied depending upon the conditions of the surfaces of the zinc sulfides. Adsorption products were analyzed after they had been removed from the surface with pyridine. Zinc dodecyl xanthate was confirmed for surfaces covered with oxidized products while dodecyl alcohol and carbon disulfide were detected on purified or weakly oxidized surfaces. It is of great significance to study the adsorbed species of collectors on the surface of sulfide minerals with a view of increasing our understanding of the mechanism of flotation. Compared with other methods, infrared spectroscopy promises to be of particular value in determining the nature of the species adsorbed at the mineral/solution interface since it gives direct identification of the adsorption products; and, furthermore, it has an advantage over the electron diffraction technique which has been employed in similar problems in that infrared spectroscopy utilizes radiation of very low energy so that the probability of changing the unstable surface films during examination should be correspondingly decreased. Infrared spectroscopic studies concerned with sulfide mineral flotation have already been reported by several investigators on zinc sulfide-hexanthi01&apos; and lead sulfide-xanthate2,3 systems. The purpose of the present study was to investigate the adsorption of potassium dodecyl xanthate (KDX) at the zinc sulfide-aqueous solution interface by means of infrared spectroscopy. Rarely is the pure zinc sulfide-xanthate system encountered in practical flotation since zinc sulfide is usually activated with small amounts of certain metallic ions, such as copper ion. However, investigation of the pure zinc sulfide-xanthate system appeared promising for studying the fundamental mechanism of the adsorption of xanthate on the sulfide minerals. Although there are few cases where xanthates having an alkyl radical higher than hexyl are employed in practical operations, KDX was used in this study since it was reported that the adsorbability of xanthate on zinc sulfide was increased with an increasing number of carbon atoms of the alkyl radicals.4 EXPERIMENTAL Samples: Experiments were made on artificial zinc sulfide and natural sphalerite. The artificial zinc sulfide was obtained commercially from Dainihon Toryo Co. as a fluorescent pigment of the purest grade A. Considering the fact that there are often cases where the surface of sulfide minerals are apt to be oxidized so that the adsorption of xanthate at sulfide mineral/solution interfaces may be substantially affected, two different procedures were employed in preparing the samples of the artificial zinc sulfide. 1) The zinc sulfide was washed with hot concentrated ammonium chloride solution (300 g per liter) to remove surface oxidation products and followed by washing with deoxygenated hot distilled water by centrifugation until the constant electric conductivity of the solution was reached (Sample I) (specific conductivity of the solution = 8.6 x l0-5 ohm-&apos; cm-&apos;). 2) Sample I in a suspension of 5% by weight was oxidized with a 1.5% aqueous hydrogen peroxide solution for about one hour, and then was washed with distilled water as mentioned in the preparation of Sample I (Sample 11) (specific conductivity of the solution = 1.0 x 10"4 ohm-&apos; cm-&apos;). Both Samples I and II were dried under vacuum and stored in a vacuum desiccator. The specific surface areas of the samples determined by the BET method using carbon dioxide gas were 19 x l04 cm2 per g for Sample I and 35 x l04 cm2 per g for Sample 11. In addition, a sample which was derived from Sample I was also prepared. In 40 ml of 3 x 10-2 M zinc sulfate solution was placed 2 g of Sample I for 2 hours, washed with distilled water by successive centrifugation until no sulfate ion could be detected and dried under vacuum (Sample 111). The purpose of this treatment will be described later. Natural sphalerite was carefully selected by hand, ground in a mechanical agate mortar for about 40

Jan 1, 1965

By W. A. Hockings, M. E. Volin, A. L. Mular

Batch grinding tests at short times were made in a laboratory rod mill with 10 x 14 mesh quartzite in corn syrup-water mixtures of varying viscosity. The weight fraction broken and size modulus were found to be independent of viscosity up to 20 cp, but at higher viscosities breakage of the feed decreased while the size modulus increased. The mechanisms of the effect of viscosity are discussed on the basis of particle dynamics. The effect of viscosity of the suspending medium on grinding has not been accorded much attention, although both wet and dry grinding are used in bene-ficiation processes and the viscosities of water and air differ greatly. schweyerl investigated the rates of grinding of quartzite in a pebble mill with air, water and glycerol as the suspending media and found the rate in terms of new surface developed per thousand revolutions of the mill to be constant and dependent on viscosity up to 20,000 rev, but to decrease and become independent of viscosity for longer grinding times. Based on considerations of the drag forces exerted on suspended particles and on the grinding media under turbulent and laminar flow conditions, viscosity can be expected to inhibit the rate of grinding in a given system as it changes the flow conditions from turbulent to laminar. The objective of this study was to determine the effect of viscosity of the suspending fluid in the batch grinding of a homogeneous feed of uniform size for short residence times, a region of more practical interest than the long times investigated by Schweyer. In actual grinding operations, the viscosity of the fluid does not change, but the consistency (apparent viscosity) of the pulp increases with additions of fines. In this study the consistency of the pulp was not measured because it was thought that the grinding times were too short to alter the apparent viscosity appreciably.* *Minus 200 mesh quartz at 65% solids has an apparent viscosity of about 25 cp as measured by a simple consistometer. Personal communication from D. F. Kelsall to A. L. Mular. For the purposes of this study, the effect of viscosity on grinding can be shown sufficiently well on the basis of the cumulative weight fraction finer than the feed size at any time, and the size modulus, ku, of the finer than feed sizes. The parameter, ku, is obtained from a form of the Gaudin-Schuhmann equation. METHOD AND MATERIAL The grinding tests were accomplished in a laboratory rod mill 10-1/2 in. long and 8 in. bore with a 20-lb rod charge consisting of two 1-in., eight 3/4-in., eight 1/2-in., and eight 1/4-in. diam rods. The mill speed was 43.2 rpm. Charges of 400 g 10 x 14 mesh Wisconsin quartzite** were ground for times of 60, **Courtesy of Minnesota Mining and Mfg. Co. 120, 180 and 240 sec in 500 cc of fluid made up of corn syrup and water in measured proportions. The temperature of the pulp was measured immediately upon completion of grinding, and the size distribution of the quartzite was determined by a wash-wet-dry screening technique. Corn syrup was chosen because of its high viscosity and ideal viscous behavior, and also because its density is not greatly different from that of water. The viscosity of each fluid mixture was measured with an Ostwald viscometer at 25 C. and a correction was made for the temperature of the pulp according to tabulated values for sucrose solutions. The density differences were so small that they probably did not significantly affect breakage. RESULTS AND DISCUSSION The conditions of the grinding tests, computed viscosities, weight fractions finer than the feed size and values of a and ku are listed in Table I. The values of a and ku were taken from the linear portions of the log-log plots of cumulative weight fraction finer vs size for the various grinding times. The plots for tests in fluids of average viscosity 8.6 cp are shown in Fig. 1. In general all of the sets of curves were linear throughout most of the size

Jan 1, 1965