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By D. M. Schuster, E. Scala

The elastic effects occurring in the matrix of a composite reinforced by discontinuous fibers were studied by means of photoelastic techniques. A hirefringent plastic was employed as the matrix material with high-strength a Al2O3 whiskers as the reinforcing fibers. It was found that for whiskers aligned parallel to the tensile load direction: (I) Matrix reinforcement occurred along the length of the whisker to within about 5 diameters of the whisker tip for a length to diameter ratio, L/D, of 40. (2) Significant stress concentrations were created in regions immediately surrounding the tips; the fine as-formed tapered ends exhibited the minimum stress concentration whereas the square-ended whisker produced relatively high values, K r 2.5 for L/D = 40. (3) The axial and radial stress distributions could he determined quantitatively; the stress distribution at the whisker-matrix interface was in general agreement with theoretical calculations. (4) The highest source of stress concentration occurred at points of fracture in whiskers which had ruptured after incorporation into the composite. Whiskers aligned perpendicular to the load direction neither reinforced nor caused appreciahle stress concentrations in the matrix. ThE properties of composites have generally been formulated empirically on the basis of macroscopic tests. There are still many questions concerning the mechanical and chemical interactions occurring at the interface between the reinforcing fiber and its matrix. Continuously reinforced plastics and dispersion-hardened metals represent the two extremes of composite reinforcement. Whether artificially produced or formed in situ, the whisker composite falls between these two extremes and is an example of discontinuous fiber reinforcement. The effect of fiber shape, size, surface condition, and end configuration on the stress distribution in the matrix is important since the presence of stress concentrations, especially in any high-strength, thin-wall structure, could become the cause of catastrophic failure. DOW,' in his theoretical discussion of discontinuous fiber reinforcement, has pointed out that appreciable stress concentrations occur at the tips or ends of the reinforcing fibers. It is the purpose of this study to examine directly, by means of the photoelastic technique, the stresses which occur in the vicinity of a discontinuity or whisker tip and to measure qualitatively and quantitatively the effects of whisker geometry when embedded in a birefringent matrix material. The use of sapphire (a A1,O3) whiskers was decided upon as the reinforcing agent because of their high elastic modulus (E- 60 X 106 psi) and in some cases strengths in excess of one and a half million psi. Sapphire whiskers are of further practical interest since they retain large fractions of their strength up to temperatures approaching the melting point (3720oF).2 The whiskers were grown, by the vapor-phase reaction commonly employed,3 as part of this study to insure a physically uniform supply. Tensile and bend tests were performed to verify that the whiskers were of the expected ultra-high strength. The high-strength whiskers can be identified and selected from the combustion boats by surface perfection, shape, and size; otherwise, strength values can vary by a factor of ten or more. Macroscopic defects are quite common on the surface of large bladed whiskers and the principal experiments were conducted with hexagonal whiskers of about 0.002 in. diameter and lengths ranging from 0.1 to 0.4 in. Upon completion of these two phases of the experiment, several birefringent resins were evaluated. A plastic, developed by Zandman,4 which is supplied by the Budd Co., was found most suitable and was used as the matrix material for the whisker composite throughout the study. It has a sensitivity of 60.5 lb per in. order, calibrated in tension and cures without introducing residual stresses. Young's modulus for this matrix material is 430,000 psi in the fully cured condition. Since good wetting and bonding between the sapphire and the matrix material is essential to the interpretation of the results, a wettability test was performed. The contact angle was measured to be 168 deg where perfect wetting is defined as 180 deg; therefore, the Budd Plastic wets the sapphire

Jan 1, 1964

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 ''high", ''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"4'6 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~' 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 J. J. Stokes

Literature on the electrolysis of aluminum from cryolite melts and on the structure of these melts is surveyed critically. Data on density, freezing point, and other properties are reviewed. Theories of the electrolysis are examined in the light of these data. Two theories are presented which account equally well for the observations. ALTHOUGH the production of aluminum is a large-scale industrial process, consuming approximately 3 pet of all of the electric current generated in this country, the mechanism of the Hall Process remains a 70-year-old mystery. It is a remarkable fact that the aluminum industry, which was established largely through research and owes much of its growth to research, still employs as its basic process the one developed by Charles Martin Hall while he was still a young man working in a woodshed. There are, of course, modifications in detail and a tremendous expansion of the size of the units used, but basically the process employs carbon anodes and a carbon-lined iron vessel as a cathode for the electrolysis of alumina dissolved in molten salt. Of the almost infinite variety of salts available, the relatively minor Greenland mineral, cryolite, 3NaF.A1F3, is still the only one which gives good performance in the electrolysis. In the early days, the process was thought of as a simple one. The dissolved alumina dissociated and, during the electrolysis, the aluminum was carried to the cathode where it was discharged and collected in a pool of metal. The oxygen was carried to the carbon anode where it reacted to form primarily carbon dioxide together with some carbon monoxide. About the only virtue that can be claimed for this hypothesis is that of simplicity. The actual mechanisms must be tremendously more complex. This paper is devoted to a rather narrow part of the whole subject, namely, what ions are present in the bath, and by what mechanism the current is carried. The complexity of the literature on this system is demonstrated in Table I, which shows the ions postulated as being present during the process. This system is not easy to investigate. Cryolite melts at about 1000°C, so that all the investigations are at relatively high temperatures. Molten cryolite fumes in air, particularly if excess aluminum fluoride is present. The cryolite changes composition on heating at 1000°C, principally by reaction with moisture in the air, but apparently also by reaction with oxygen. Cryolite reacts with most of the customary materials of construction, and those that are not attacked by cryolite seem inevitably to react with molten aluminum. Graphite is the only common material that is inert to the electrolytic bath. Pure cryolite can be held in platinum. There is hope that some of the newer refractories will stand up in bath, and their development for this purpose would be a major advance in the field. The techniques to be discussed, then, are not the most advanced ones. Rather, they are examples of old standardized methods applied under difficult conditions. The principal methods that shed real light on the mechanism are density, electrical conductivity, freezing-point lowering, transport number, viscosity measurements, and reactivity of bath with carbon dioxide. The first measurement to be discussed is density. This procedure is relatively straightforward. A hollow platinum bob is suspended by fine platinum wire from an analytical balance into the melt being investigated. Density1-4 of the system sodium fluoride-aluminum fluoride is shown in Fig. 1. There is a maximum in the density near the cryolite composition, but actually the maximum is on the NaF-rich side of cryolite, close to the composition NaF - Na3AlF8. Density measurements are also useful in giving a clue to the nature of cryolite-alumina melts.1, 4 On the first addition of alumina, density decreases, Fig. 2, although the density of alumina, either solid or liquid, is higher than that of cryolite. These density results indicate that the systems are not simple. A great deal of effort has been spent in measuring the electrical conductivity of molten cryolite and of cryolite with various additives. Conductivity measurements are quite easy for fused salts that can be measured in a dip cell, but no successful dip cell has been made available yet for cryolite. Recourse is had

Jan 1, 1959

By K. W. Smith, E. A. Thomas

Various grades of synthetic mullite have been developed in recent years to replace or supplement natural sources of mullite deriued from the mullite group of minerals consisting of sillimanite, kyanite, and andalusite. Raw materials and heat treating processes used in making synthetic mullite are described. Chemical and physical data are given for typical grades and crystalline structure is illustrated with micrographs. Use of synthetic mullite as a refractory material in the glass and metallurgical industries is discussed. Mullite (3A12O3.2siO2), the only stable compound formed in the alumina-silica system, is usually present to some degree in all aluminum silicate ceramic products. The formation of mullite is considered beneficial to give rigidity to the structure and is dependent upon the ratio of Al2O3 to SiO2 in the original composition, particle size, degree of mixing, firing temperature, cooling rate, and the presence of auxiliary glass-forming fluxes. Mullite may also be formed at the reaction interface of fire clay or alumina-type refractories in contact with glass or slag melts. The term synthetic mullite is commonly used today to identify a class of sintered and fused aggregates or grains in the alumina-silica system having a highly developed mullite structure but derived mainly from raw materials other than the sillimanite group of minerals. Within the past 15 years extensive research has been done to develop economical processes to form sintered synthetic mullite aggregate to replace calcined Indian kyanite in super-refractories. Severa1 brands of such mullite are now being produced in commerical quantity and finding extensive use in refractories. Based on the service results of such refractories in many applications throughout the metallurgical, ceramic, and glass industry these developments have been considered successful and suitable substitutes for Indian kyanite now appear assured. EARLY DEVELOPMENT The conversion of kyanite, sillimanite and anda-lusite minerals of the sillimanite group to mullite and their use in refractories and porcelain have been discussed quite extensively in the literature by peck,' Grieg,' Riddle and Foster,3 Bowen and Grieg,4 and others and will only be mentioned here for reference to compare properties with synthetic mullite. In 1928, curtis5 reported on the development of a high temperature gas-converter process for forming synthetic mullite. The raw materials were derived mainly from lumps of high alumina clay of the correct natural composition or blends of clays and alumina that was interground and briquetted to form a suitable charge to maintain a surface combustion firing within the converter. Curtis was, no doubt, the first to illustrate by micrographs in natural color the crystalline structure of mullite derived from kyanite and mullite derived by sintering clay and alumina mixtures at temperatures above cone 32 (3123°F) and by electric fusion. In 1937, sei16 was issued a patent covering the use of a mixture of alumina-silica minerals and alumina in the proportion to form a mullite-yielding material at temperatures in excess of 3100' F. During the period from 1930 to 1940, economic conditions were not favorable for the production of synthetic mullite mainly due to an adequate supply of good grades of Indian kyanite ore suitable for conversion to mullite. Uncertain conditions on availability of the Indian kyanite during the early stages of World War II fostered further study on the development of synthetic substitutes. In 1943, McVay and wilson7 reported on an extensive investigation of domestic substitute materials. Their work covered essentially the use of mixtures of electric furnace mullite, calcined topaz, and calcined domestic kyanite. Compositions were found that gave equivalent or better hot load strength than Indian kyanite in mullite-type brick compositions; however, the calcining of the topaz presented certain physical and chemical problems on the disposition of silicofluoride and hydrofluoric acid while the high cost of electric furnace mullite was a limiting factor. In this work it was pointed out that water-quenched fused mullite was found to be unstable on reheat and gave poor hot load strength due to excessive glass present whereas the slow cooled or annealed mullite contained large crystals of mullite and corundum with little glass and gave superior results.

Jan 1, 1961

By R. M. N. Pelloux

This study of aluminum-copper alloys had two aims: 1) To determine the effect of the amount and distribution of a second phase, CuAl2, on the creep-rupture strength, ductility, and fracture characteristics of the alloys. The work of Gemmell and grant' on single-phase aluminum-copper alloys provided a basis for the present study. 2) To attempt to provide a relation between the microstructure and strength of two-phase alloys deformed at comparatively high temperatures (greater than 0.45 T,). The creep behavior of the two-phase magnesium alloys Mg;Ce and Mg-A1, has been treated by Roberts. 9 In work reported by Sully and Hardy4 and by Underwood, Marsh, and Manning~ on A1-Cu two-phase alloys, and also in a portion of the work of Gemmell and grant,' aging took place during the creep tests. 'In the present work, overaged aluminum-copper alloys were subjected to creep deformation at two temperatures, 500 and 700OF. The overaging treatments to produce the precipitate dispersions were performed prior to the test, at temperatures which were the same as the ultimate respective test temperatures. Hence, the present study is concerned with the creep behavior of stable (in contrast to "underaged") two-phase A1-Cu alloys, i.e., alloys in which no depletion of the solid-solution matrix occurred during: creep. MATERIALS AND PROCEDURE A 2 and a 3 pct Cu alloy, supplied by Alcoa, were studied; Table I shows the compositions. The grain size of the specimens, 0.9 to 1.0 mm, was achieved by annealing the machined test bars for 2 hr at 1000°F, followed by furnace-cooling to 900°F, and homogenizing for 4 hr. Both compositions are in the single-phase condition at 900°F. Two types of overaged dispersions, termed "over-aged I" and "overaged 11" were prepared after the grain size and the homogenization anneals. The overaged I alloys were prepared by quenching to room temperature after homogenization, aging at either 500' or 700°F for 72 hr, and air-cooling to room temperature. The overaged I1 alloys were prepared by furnace-cooling after homogenization, to either 500' or 700°F, and holding at the necessary temperature for 72 hr. The times for furnace-cooling from 900°F to 700° and 500°F were, respectively, about 2 and 3.5 hr. The structures of the A1-2 pct Cu alloys are shown in Fig. 1 (overaged I) and in Fig. 2 (overaged 11). A comparison of Figs. 1 and 2 shows that in the overaged I alloys the precipitate particles along the grain boundaries are much more closely spaced and the grain boundaries are straighter than they are in the overaged I1 alloys. Further, the particle size and spacing in the grains are smaller than in the overaged I1 alloys. Microstructures of the A1-3 pct Cu alloys have not been shown; the structures of these alloys differed from those of the A1-2 pct Cu alloys only in that the distribution density of the particles was greater. The creep specimens had a gage section 1 in. long with a diameter of 0.155 to 0.195 in. Before testing, specimens were electropolished in a solution of 100 cc glacial acetic acid, and 30 cc of 60 pct perchloric acid, at 40' to 50°F, at 24 v. The specimens were kept refrigerated prior to testing to avoid precipitation at room temperature. Constant stress creep tests were conducted; the load was applied 75 min after heating of the specimens to test temperature had begun. EXPERIMENTAL RESULTS Creep-Rupture—Fig. 3 shows the log stress-log rupture life plotfor the overaged alloys studied, and also for the underaged A1-2 pct Cu alloy.' At 700°F, the stress-rupture life relationship is nearly independent of both the amount of precipitate (i.e., composition) and of the type of overaging treatment (i.e., precipitate dispersion). At 500°F it is apparent that the increase in rupture life that was ex-

Jan 1, 1960

By D. L. McDanels, J. W. Weeton, R. W. Jech

An investigation was conducted to determine the stress-strain behavior and tensile properties of metallic composites and to relate them to the properties of the base materials. Tungsten fibers in a copper matrix were chosen as the model sys-tem to investigate these properties. Room-temp-atzcre tensile and dynamic -modulus tests were used To meet the demand for improved structural materials, considerable effort is being directed toward the creation of composite materials. One such material under investigation is the fiber-reinforced composite, in which a ductile, relatively weak matrix is reinforced with high-strength fibers. Some work has been done on the reinforcement of metallic matrices with metallic fibers1"5 as well as with ceramic-whisker reinforcement. Summaries of much of this work have been published by Mach-lin7 and Baske~.' Work done at the Lewis Research Center of NASA-" has involved the making and testing of composites composed of a fiber, tungsten, and a matrix, copper, which were insoluble in each other. An equation was presented that showed the relation between the ultimate tensile strength of the composites and the strengths and relative volume percents of the components. This relation was verified experimentally for composites containing fibers extending the full length of the specimen as well as for composites reinforced with short-length or discontinuous fibers. Since the publication of the preliminary results,9'10 additional data have been obtained. This paper presents these data as well as analyses of the stress-strain behavior and the mechanics of deformation of uni-axially oriented, fiber-reinforced metallic composites, in which both components are mutually insoluble. EXPERIMENTAL PROCEDURE Composites were made with high-purity copper as the matrix and 3-, 5-, and 7-mil-diam tungsten wire as the reinforcing fiber. Some specimens were made in which the reinforcing fiber extended completely through the full length of the composite test section. The fibers were placed in ceramic to determine these properties. The composites were reinforced with either continuous or discontinuos tungsten fibers. The tensile properties and stress-strain behavior of composites reinforced with either type of reinforcement were similar, and in both cases the full strength of the fiber was utilized. tubes to insure axial orientation and infiltrated with copper at 2200°F for 1 hr. Composites were also made with short-length (3/8 in. long) 5-mil-diam tungsten fibers as discontinuous reinforcement and infiltrated under the same conditions. The reinforcing fibers in both cases were longitudinally oriented in the direction parallel to the tensile axis. Room-temperature tensile tests were conducted on the composites, stress-strain curves were obtained, and ultimate tensile strength and elongation were measured. Dynamic modulus of elasticity, based upon the resonant frequency induced in the flexural mode of vibration, was also determined for the composites and the components. A more detailed discussion of the experimental procedure employed in this investigation may be found in Ref. 11. RESULTS Room-temperature tensile tests were conducted on 3-, 5-, and 7-mil-diam tungsten wires which had been annealed for 1 hr at 2200°F and show the tensile strength of the wires to be 331,000, 327,000, and 290,000 psi, respectively. Since all the composites were infiltrated under these conditions, the strengths were considered to represent the strength of the fibers in the composites throughout this study. The average tensile strength of the annealed copper used as the matrix in this investigation was 27,800 psi. Results of room-temperature tensile tests on composites reinforced with 3-, 5-, or 7-mil-diam tungsten fibers are plotted as functions of composition in Fig. 1. These data represent previously reported datag,l0 as well as data more recently obtained. The line shown on each curve represents a prediction of tensile strength as a function of composition; the calculation of this line was explained in Refs. 9 and 10. A similar plot is presented in Fig. l(d) for composites reinforced with short-length, discontinuous 5-mil-diam tungsten fibers. Again, both the previously reported and the recent data are presented, and the line shown is identical to that shown for

Jan 1, 1965

By A. R. Troiano, R. F. Hehemann

The influence of partial decomposition to high temperature bainite on reaction kinetics at a lower temperature has been studied in two alloy steels. Reaction at the lower temperature is retarded by the prior treatment, and the extent of decomposition may be reduced. Interpretation of these results is based on a mechanism involving a limitation in the nucleation and growth of bainite plates. OF the major transformations in steel, the characteristics and general behavior of the bainite reaction are probably the least understood and appreciated. Limitations of space preclude a critical evaluation of the present status of the bainite transformation in this presentation; however, such a treatment will shortly appear elsewhere. Only the salient features pertinent to the present investigation will be introduced briefly here. Although the reaction curve for the formation of bainite is similar to that for a nucleation and growth process, other kinetic features are more in keeping with the martensitic mode of transformation. A definite temperature exists above which austenite will not transform to bainite.1-5 his temperature, which has been designated B., is determined by the composition of the austenite. Unlike other nucleation and growth processes, the amount of austenite transformed to .bainite is a function of reaction temperature. The extent of decomposition increases from 0 at H. to 100 pct at some lower temperature.' , This lower temperature will be designated B1 and appears to be relatively insensitive to austenite composition.% 5 The similarity in the effect of reaction temperature on the bainite and martensite transformations serves to emphasize the close connection between these two decomposition processes. Austenite decomposition in the bainite range proceeds without partition of the alloying elements.8-11 Partition of carbon has been proposed" primarily on the basis that partial transformation to bainite lowers M, and increases the amount of austenite retained at room temperature. Carbon enrichment resuslting from such partition has been employed to explain the influence of reaction temperature on the extent of decomposition.'" It should be noted, however, that no enrichment has been detected experimentally in high carbon steels.1,14,15 Lattice-parameter measurements of retained austenite in steels containing 0.3 to 0.4 pct C have indicated carbon enrichment, 3,10-18 although the split indicative of a high carbon martensite has not been reported. Carbon enrichment, if it does occur, must be highly localized around the bainite plates. Therefore, carbon enrichment does not account for the influence of temperature on the progress of the bainite reaction."' Thermal history is known to influence the martensite transformation through stabilization.20,21 No similar phenomenon in the bainite transformation has been reported. Materials and Procedure Two triple-alloy steels were chosen for this investigation. Their compositions were as given in Table I. These steels were chosen because the pearlite reaction did not interfere with the bainite reaction. Steel K was received in the cast condition and forged from 2 in. square bars to 1/2 x1 3/4 in. plates. The 4340 was received as 11/4 in. hot-rolled rounds. Both steels were homogenized in vacuum for one week at 2300°F in order to minimize segregation. A quenching dilatometer similar to that described by Flinn, Cook, and Fellows" was employed for the kinetic measurements. Dimensional changes were detected by a differential transformer coupled with a high speed recorder. The dilatometer was mounted so that it could be transferred to any one of three furnaces: a nitrogen-atmosphere austenitiz-ing furnace and two salt-bath furnaces for isothermal transformation. Dilatometer specimens were 1/32 x 1/4x 1/2 in. with a gage length of 1.4 in. All specimens were nickel plated in order to minimize decarburization during austenitizing. The austenitiz-ing conditions consisted of 10 min at the temperatures given above. Austenitizing temperatures were controlled to 210°F and transformation temperatures to ±3ºF. The precision of the dimensional measurements was estimated to be ± 5 x105 in. per in. Results and Discussion Isothermal Transformation: The characteristics of the isothermal bainite reaction will be described

Jan 1, 1955

By E. Martinez

Samples of chrysocolla, a hydrated copper silicate, from several sources were submitted to differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). Pure samples of chrysocolla are difficult to obtain, but comparison of the thermograms revealed that certain reactions occurred in all the samples and it is believed that these are due to chrysocolla. Endothermic reactions occurred at 50' to 175°C, 350° to 650°C, and 980° to 1100°C each of which caused a weight loss. The first was due to loss of absorbed water, the second to a dehydroxyla-tion, and the last to conversion of cupric oxide to cuprous oxide. In addition, two exotherms were detected at 685° to 695°C and 935° to 950°C. Infrared spectra of heated samples indicated the exotherms were due to changes in the Si-O bonds leading to the formation of cristobalite. The results suggest that thermoanalysis may be a more sensitive and reliable method for detection and identification of chrysocolla than X-ray diffraction, infrared spectroscopy, or optical techniques. The recovery of copper from oxide ores has been the subject of much research in recent years. One of the principal oxide copper minerals is chrysocolla, a hydrated copper silicate. The information available indicates that it has widely varying properties depending on the origin of the sample. Chrysocolla usually is found associated with cuprite, malachite, azurite, and native copper. Most of these other minerals are recoverable by present day flotation practice, but chrysocolla is lost in the tailings.1,2 Reagent combinations that are successful in laboratory chrysocolla flotation with ore from one source have been found to be ineffective with another. 3 The copper segregation process offers an altemative to beneficiation of oxide copper ores.4'5 The process is of particular interest in processing ores that cannot be treated by conventional hydrometal-lurgical methods because of high acid consumption.6 Fuller understanding of the properties of chryso- colla may prove of value in the search for improvements in both the flotation and segregation processes. Chrysocolla samples from Arizona, Nevada, Chile, Australia, and South Africa were studied by differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). In addition, a sample from Miami, Ariz., was submitted to X-ray diffraction, infrared spectrophotometry, and surface area determination. EQUlPMENT Differential thermal analysis (DTA) detects, amplifies, and records exothermic-endothermic reactions occurring in a sample as its temperature is raised at a constant rate, usually 10°C per minute. A unit made by the Robert L. Stone Co. was used in this study. The tests can be run if desired with a gas streaming through the sample. A thermobalance records weight losses or gains in a sample as its temperature is raised at a uniform rate. The gravimetric analyses (TGA) were run on a Chevenard thermobalance converted electronically for graphic recording. A heating rate of 5°C per minute up to 1100°C was used in these tests. A Perkin Elmer Infrared Spectrophotometer, Model 221, was used with sodium chloride optics obtaining IR spectra in the 2 to 15 region. A pressed pellet technique with potassium bromide was used in preparing the samples. DESCRIPTION OF SAMPLES Chrysocolla is found in the oxidation zones of copper deposits commonly associated with malachite, azurite, and limonite. It is described as varying in composition and in color from bluish green to brown or black. Inclusions of other minerals are usual so chemical analysis of chrysocolla samples may be suspect. However, it is considered by many to be a solid solution of CuO, SiO2 and H2O with a general formula of CuO.SiO2.2H2O or 2CuO.2SiO2. 3H20. Chukhrov7 has described a sample from the Urals as CU3,5(OH)2 (A1Si3) O10.nH2O and stated that chrysocolla is a montmorillonite-type mineral. On the basis of X-ray analyses, DTA, and infrared spectra of chrysocolla from the Inspiration Mine, Ariz., Sun8 concluded that there was no substantial evidence to classify it as a montmorillonite mineral. Chrysocolla samples from many sources throughout the world were used in this investigation. The following is a brief description of each:

Jan 1, 1963

By R. J. Charles

SEARCH for a consistent theory to explain the relationship between energy input and size reduction in a comminution process has accumulated, over the years, an enormous amount of plant and laboratory data. Although some correlation of these data has been possible for purposes of engineering design and for the advancement of research in fracture, there is still great need of a means of predicting behaviour of a solid when it is reduced in size by mechanical forces. The best known hypotheses proposed to describe the energy-size reduction relationships in crushing and grinding stem from a common origin. The present article analyzes problems of comminution in the light of the precepts of this origin. Its object is to reconcile points of difference between these well known hypotheses and to present relationships more widely applicable to comminution studies. Theoretical Considerations: Most existing relationships between energy and size reduction of a brittle solid stem from a single, simple, empirical proposition.&apos; Although this proposition can be demonstrated by observation and experiment, no theoretical derivation is yet possible. Mathematically, the proposition may be stated as follows: dE = -Cdx/xn [1] where dE = infinitesimal energy change, C = a constant, dx = infinitesimal size change, x = object size, and n = a constant. Eq. 1 states that the energy required to make a small change in the size of an object is proportional to the size change and inversely proportional to the object size to some power n. No stipulations are placed on the exponent n in either magnitude or sign. In 1867 Rittinger2 postulated that the energy required for size reduction of a solid would be proportional to the new surface area created during the size reduction. As far as can be determined there is as yet no physical basis for Rittinger&apos;s hypothesis. Rittinger&apos;s hypothesis can be stated mathematically as follows: E, = K(oa-a-0 . [2] Er = energy input per unit volume, K = a constant, <ti = initial specific surface, and o2 = final specific surface. In the size reduction of particles of size x, to particles of another smaller size, x2, Eq. 2 becomes the well known relation: ET = K&apos; {l/x2-l/xx) [3] where K&apos; is a constant. Eq. 3 may be arrived at from the proposition given in Eq. 1 by integrating and by assigning a value of 2 to the exponent n. J dE = J - C dx/x2 E = Kt (1x - 1x) where K&apos; = C. In 1885 Kick3 proposed the theory that equivalent amounts of energy should result in equivalent geometrical changes in the sizes of the pieces of a solid. For example, if one unit of energy reduced a number of equal-sized particles to particles of one half the size, then the same amount of energy applied to the particles resulting from the first test should result again in a size reduction of one half or a final size one quarter the original size. The Kick concept may be expressed as follows: Ek = K" log x1/x2 [41 K" = a constant and E, = energy per unit volume. The expression for Kick&apos;s law may be arrived at by again integrating Eq. 1 and in this case assigning a value of 1 to the exponent n. dE= J - C dx/x Eh = - C In {x/x2) = K" log (x,/x,) where K" = 2.3 C. Application of Kick&apos;s and Rittinger&apos;s laws to comminution has met with varied success. Gross and Zimmerley4 and Piret5 have shown that Rittinger&apos;s equation applies under certain conditions of experimentation. Walker and Shaw6 express the belief that in metal turning and shaping and in grinding of both metals and minerals the production of very fine particles (less than lP) follows Kick&apos;s hypothesis, whereas Rittinger&apos;s concept is valid for the size reduction of coarse particles. For the practical case of crushing and grinding, however, neither of the above hypotheses has received general acceptance. Bond&apos; has lately proposed that since neither Kick&apos;s nor Rittinger&apos;s hypotheses seem correct for plant design work, an energy-size reduction relationship somewhere between the two would be more applicable. The fundamental statement of Bond&apos;s work

Jan 1, 1958

By H. C. Casey, M. B. Panish

The roles of the phase diagram and the diffusion and solubility analyses in the selection of sources for the diffusion of zinc into GaAs are discussed. Isothermal sections of- the phase diagram are described at 1000°, 775°, 744°, and 700°. Below 744° the three solid phases, Zn3As2, GaAs, and ZnAsz, may be in equilibrium. In the composition regions where the three solid phases are in equilibrium, the partial pressures of the components do not vary with composition and there is no liquid phase. A diffusion source composition within that region containing 5, 50, and 45 at. pct Ga, As, and Zn was selected to yield reproducible diffusion profiles without surface damage. The 5/50/45 ternary source Provides a significant improvement in the reproducibility and planarity of- the zinc diffusion as compared with other zinc diffusion sources that result from starting with elemental zinc, dilute solutions of zinc in gallium, or various combinations of zinc and arsenic. Several experimental diffision profiles for the 5/50/45 diffusion source have been determined. The profiles are very steep in the region of the junction and produce devices that exhibit step junction behavior. The junction depth varies as the square root of time. Diffusion at 700°C for 4 hr gives a 5-µ junction depth and a surface concentration of 2.4 x1020 cm-3. The surface concentration is enhanced by a factor of three and the junction depth decreased by a factor of ten as compared with diffusion with a starting source 01- elemental zinc. The differences in dijyusion behavior with these two sources are due primarily to the approximately 10&apos; greater equilibrium As4 partial pressure for the 5/50/45 source. ThE most common technique for the preparation of GaAs p-n junctions for diverse applications ranging from switching diodes to injection lasers has been to diffuse zinc into the solid from the vapor phase. The zinc impurity has generally been provided by introducing into a diffusion ampoule elemental zinc, dilute solutions of zinc in gallium, or various combinations of zinc and arsenic. For the purpose of eliminating surface deterioration, zinc has been diffused into GaAs through SiO2 films1 and from zinc-doped SiO2 films.2 During a study of the injection and recombination mechanisms in GaAs junctions, we found that these diffusion techniques either resulted in nonreproducible diffusion profiles and nonplanar junction interfaces or were extremely inconvenient to use. An unpublished report by Allen and pearson3 emphasized that an understanding of diffusion requires relating the diffusion conditions and system compositions to the ternary phase diagram. Recent studies have made it possible to relate the effect of starting source composition on the GaAs sample surface and diffusion profile reproducibility and, in addition, to estimate the expected surface concentration and zinc diffusivity. These studies include the Ga-As-Zn phase diagram,415 the determination of the incorporation reaction for zinc as a substitutional impurity,6 and the analysis of the concentration dependence of the diffusion coefficient.&apos; In this paper the role of the phase diagram in the selection of the starting diffusion source composition is illustrated, and an application of the diffusion and solubility analyses is used to demonstrate their utility in the estimation of surface concentration and diffusivity for various starting source compositions. Consideration of the isothermal sections of the ternary phase diagram shows that below about 744° C a composition region exists where the three solid phases Zn3As2, GaAs, and ZnAs2 are in equilibrium without a liquid phase. In this region the partial pressures of the components do not vary with composition, and thus the surface concentration and diffusivity depend only on temperature. A diffusion source composition within that region containing 5, 50, and 45 at. pct Ga, As, and Zn was selected. As will be described in detail, this diffusion source yields reproducible diffusion profiles without surface damage, planar junction interfaces, and steep profiles that result in devices with step junction behavior. Only closed diffusion systems are considered. Open or flowing vapor systems require the maintaining of constant vapor pressures in the flowing gas and represent control problems outside the scope of this discussion.

Jan 1, 1969

By Pradeep K. Rohatgi, David N. French, Surendar M. Jain, Clyde M. Adams

The effect of solute concentration and diffussivity on dendritic solidification of dilute binary aqueous solutions has been investigated; chlorides of sodium, potassium, lithiurn, and hydrogen were used as solutes. Dendrite spacings were measured in spherical droplets and in unidirectionally solidified specimens. In the droplets, the freezing rate is uniform over the entire specimen and remains constant from the beginning to the end of solidification. In the unidirec-tionally frozen specimens the freezing rate varies within a given volume of liquid during the solidification cycle; in addition, it varies with location uithin the specimen. Mass transport analysis has been used to calculate the supersaturation, AC, supercooling, AT, and transcerse growth velocity, V , of ice dendrites during solidijication from the dendrite spacings measured in the droplels. The ice dendrite spacing in a given solute increases lineary with the solule concentralion at a fixed freezing rate. The ualues of AC, AT, and V increase with an increase in solule concentration. The value of AT in the aqueous solution is of the same order of magnitude as in Al-Cu alloys of the same concentration; the dendrite spacings in Al-Cu alloys also increase with an increase in solute concentralion. For the jamily of aqueozrs solulions incestigaled, the dendrite spacing increases linearly with solute diffusivity at fixed values of concertralion and freezing ,rate. The values of ?C and ?T decrease, whereas the value of V increases with an increase in solule diffusicity. The measured dendrite spacings , L, can be expressed by the relatiun: L = K;(dfa/db) 4 K2C +K3D - K4 where dfs/d? is-change in fraction solid with time (freezing rate), C is solute concentration, D is solute diffusivit K1 = (14 * 4)pmin1&apos;2, K2 = (70 ± 10) pl (moles)- K3 = (24 r 3) . l05 psec (cm)-~. K. = -132 ± 10) 1. FREEZING of solutions is almost always an ehunmix-ing" process because the composition of crystallizing solid generally differs from that of the parent liquid. " Solute concentration and transport are therefore in]portant considerations in solidification of solutions. The influence of these factors on the dendritic solutions produced from metallic solutions is of practical significance since the properties of the solid aggre-gate are often strongly influenced by dendrite spacing.&apos;&apos;&apos; Alexander and Fthines3 found that dendrite spac- ings generally increase with solute concentration in several metallic systems. Michael and Bever1 have observed an increase in a aluminum dendrite spacings in dilute A1-Cu alloys. Rohatgi and AdamsJ have reported a linear increase in a aluminum dendrite spacings with increasing copper contents up to 28 pct in A1-Cu alloys. Bolling and Tiller"&apos; have theoretically examined the effects of solute concentration and diffusivity on the growth of cells and dendrites. Their analysis of dendritic growth assumes a steady-state growth and the maximum possible velocity for dendrite propagation. In addition, the quantitative analysis is restricted to dendrites of rotational symmetry and is therefore not directly applicable to the plate-shaped dendrites of ice obtained in the present study. There are practically no experimental observations of the effect of solute diffusivity on dendrite spacings in metallic systems. The reason appears to be the lack of experimental data on solute diffusion coefficients in liquid metallic solutions. The present work is concerned with the effect of solute concentration and diffusivity on dendritic solidification of dilute aqueous solutions: the solutes examined are potassium chloride. sodium chloride, lithium chloride. and hydrogen chloride. There were several reasons for selecting these solutes. The variation of dendrite spacing with freezing rate in these solutiolls is similar to that observed in A1-Cu alloys.8 These aqueous solutions have almost identical phase diagrams at dilute concentrations. Fig. 1. and the diffusion coefficients show very little variation with solute Concentration.9,10 Dendrite spacings were measured as a function of freezing rate. solute concentration. and solute diffusivity. Dendrite spacings were measured in two different types of freezing systems. droplet and unidirectional, respectively. In the droplet freezing system

Jan 1, 1970

By V. Koump, T. F. Perzak, R. G. Olsson

The rate of dissolution of recrystallized alumina in molten iron oxide in equilibrium with iron at 1450°C was studied by rotating alumina disks in the melt. The samples were rotated from 1 to 12 min at speeds from 54 to 3270 rpm. It is concluded from the experimental results that the process is limited by diffusion in the liquid boundary layer. The interdiffusion coefficient for the dissolution of alumina disks in pure molten iron oxide was estimated to be about 3 xl0-5= sq cm per sec. THE erosion of refractory materials is of considerable importance in iron- and steelmaking processes. Since many refractories contain alumina, this investigation was undertaken to develop a further understanding of the erosion mechanism. Shurygin et al.1-3 have investigated the rate of dissolution of alumina in molten silicates and molten fluorides by rotating alumina disks in various melts. The rates were reported to be limited by diffusion in the liquid boundary layer. In the present investigation the rate of dissolution of alumina in molten iron oxide in equilibrium with iron was studied in a similar manner; alumina disks were rotated at different speeds in molten iron oxide at 1450°C. The relationship between the rate of dissolution of the flat surface of the disk and the speed of rotation was used to determine whether the process is limited by diffusion in the liquid boundary layer or by some chemical reaction mechanism. APPARATUS AND EXPERIMENTAL PROCEDURE A schematic diagram of the experimental apparatus is shown in Fig. 1. The iron oxide melts were contained in 2-in.-diam high-purity iron crucibles that were centered in a cylindrical graphite susceptor. Prior to each sequence of experiments, sufficient reagent-grade ferric oxide was added to a crucible to form approximately 350 g of molten iron oxide; the depth of the melt was about 11/2 in. To prevent excessive erosion of the crucible, about 70 pct of the required iron was added to the crucible in the form of iron powder. The mixture was melted in an atmosphere of purified argon by induction heating with a 250-kc generator. After the oxide was molten, a Pt/Pt-10 pct Rh thermocouple at the exterior of the crucible was calibrated against an iron-sheathed thermocouple immersed in the melt and was thereafter used to regulate the melt temperature. All experiments were conducted at 1450°C with a probable error of 10°C. The alumina disks were constructed from pure re-crystallized alumina having a density of 3.7 g per cu cm (porosity approximately 6 pct). For each disk sample a 1-cm-diam alumina cylinder of known length (0.9 to 1.0 cm) was cemented into a ground seat at the end of a 1.27-cm-OD centerless ground alumina tube. The ends of the tube and cylinder were flush and served as the disk surface. When mounted in the apparatus the alumina tube was guided by tungsten carbide bearings and rotated by a variable-speed motor. The bearing and drive assembly could be raised and lowered in order to allow the sample to be quickly moved in and out of the melt. At the start of an experiment, a sample was preheated for several minutes directly above the melt, and then immersed in the middle of the melt to a depth of a in. and rotated for 1 to 12 min at speeds of 64 to 3270 rpm. The speed of rotation was measured by a hand tachometer. At the start and completion of each experiment, a melt sample was withdrawn with a cold copper rod and the alumina content was determined by chemical analysis. During individual experiments the alumina concentration of the melt changed by the order of 0.25 wt pct. Average melt compositions for individual experiments were used in the subsequent computations and were in the range between 0.12 and 4.3 wt pct alumina. The extent of dissolution was determined by sectioning the end of the sample and measuring the final length of the alumina cylinder with a microscope. Since the exposed end of the cylinder, i.e., the disk surface, was etched in a manner characteristic of this geometry, a number of measurements were made on

Jan 1, 1969

By R. E. Pray, M. C. Fuerstenau, J. D. Miller, B. F. Perinne

Quartz cannot be floated with potassium amyl xanthate as collector at any pH. Complete flotation is achieved with certain minimal additions of amyl xanthate and Pb from pH 5.8 to 8.5 and with amyl xanthate and Zn from pH 7.5 to 8.1. The active species of these metal ions responsible for activation are shown to be PbOH and ZnOH No flotation was effected when Cu and Mg were added as activators. Previous work1,2,3,4,5,6,7 has shown that quartz may be floated in the presence of sulfonate or soap when the following two criteria are met: 1) some portion of the added metal ion has hydro-lyzed to its first hydroxy complex, and 2) a precipitate of the metal-collector has formed. Since sulfonate and soap, two substantially different anionic collectors, conform to these criteria, this phenomenon may well be expected to be of a general nature. In this view then, it would appear that any anionic collector, including xanthates, should also float quartz when these two criteria are met. The object of this paper is to demonstrate the conditions under which quartz will respond to flotation in the presence of potassium amyl xanthate. EXPERIMENTAL MATERIALS AND TECHNIQUES Quartz was prepared by leaching the sized sample (48 x 150 mesh) with HC1 until no iron could be detected in the leach liquor. Conductivity water, made by passing distilled water through an ion exchange column, was used in the investigation. Potassium amyl xanthate was selected as collector. Purification of this reagent was effected with the following method: 1) a laboratory sample of potassium amyl xanthate was dissolved to saturation in hot ethyl alcohol and filtered several times while still hot, 2) the filtrate was cooled, during which time potassium amyl xanthate crystallized out of solution; the xanthate was then separated from the solution by filtration, 3) the amyl xanthate was dissolved in fresh hot ethyl alcohol and filtered, 4) step (2) was repeated, 5) the crystalline potassium amyl xanthate was washed with ethyl ether five times, and 6) the xanthate was dried for 24 hours under continuous vacuum. Inorganic impurities are insoluble in hot ethyl alcohol whereas dixanthogen is soluble in ethyl ether. Five-gram charges of 48x150 mesh quartz were conditioned for 3 min in 125 cc of solution containing the reagents and were floated with the small-scale cell and procedure described in previous papers.478 Reagent grade HCl and NaOH were used for pH adjustment, while reagent n-amyl alcohol was added as frother. Frother addition is necessary with this technique, but it should be mentioned that data, similar to those shown in Fig. 2 for 1 x10-4 mole per liter Pb++ and 1 X 10-4 mole per liter AX-, were also obtained with a Hallimond cell in the absence of frother. EXPERIMENTAL RESULTS Clean quartz could not be floated with amyl xanthate at any pH. Flotation was achieved under certain conditions, however, when various metal ions were added to the system. The activating ions used were lead, zinc, copper and magnesium, added as reagent grade chloride salts. Lead as Activator: The effect of Pb++ as activator was examined at five different additions of amyl xanthate (Fig. 1, 2 and 3). When 1x 10-5 mole per liter xanthate was added in the presence of 1 x 10"4 mole per liter Pb ++, no flotation was obtained at pH 6.5 or below, while a recovery of about 60% was effected at pH 7. When the pH was increased to 7.8, no flotation was again obtained, Complete depression was noted from pH 7.8 to about 10, at which point a recovery of about 30% was achieved. At about pH 11, the precipitate of lead amyl xanthate which was present below this pH dissolved and complete depression occurred. When 2.5x 10-5 mole per liter xanthate was added with the same lead addition, no flotation was obtained at pH 5.8 and below, whereas a recovery of

Jan 1, 1965

By F. V. Lenel, G. S. Ansell, J. A. Dromsky

The growth of aluminum oxide particles in a nickel matrix was studied eve?. the temperature vange of 2140° to 2470°F. The instability of the dispersed alumina was shown to be independent of the crystal structure of the alumina. The activation energy for the growth of the dispersed alumina was found to be 84.7 1 2.0 kcal. The particle radius increased as a function of time. These results indicate that the growth is not diffusion controlled. It is believed that the rate controlling mechanism is the dissolution of the aluminum and oxygen atoms into the nickel lattice. THE strength properties of alloys which consist of a finely dispersed second phase in a metallic matrix depend upon the spacing between the second phase particles. It is therefore desirable to achieve very fine dispersions in these alloys. Furthermore, to retain the properties these very fine dispersions must be stable during fabrication and service of the alloys. The best known of the dispersion strengthened materials, the SAP type alloys, which consist of a dispersion of aluminurn oxide in aluminum, have exceptionally good stability up to the melting point of aluminum. There is evidence, however, that other dispersion strengthened alloys, even those consisting of refractory oxides in a metal matrix, may be less stable. This investigation is concerned with the stability of Ni-Al2O3 alloys in the temperature range in which these alloys are usually fabricated. The mechanical properties of Ni-Al2O3 alloys at elevated temperatures have been previously investigated by Crelnens and rant,&apos; and Gregory and Goetzel.2 The behavior of these alloys in stress rupture tests appears to indicate that at temperatures below 1800°F they are highly stable. There is some doubt, however, as to their stability at the higher temperatures used during the conventional fabrication. Cremens and Grant, in preparing their test alloys, cousolidated, by powder metallurgical techniques, nickel powders as fine as 0.13 µ diam and alumina powders as fine as 0.018 µ. Metallo- graphic examination of the alloys following fabrication revealed that none had interparticle spacings of less than 2 µ. Considering the size of the original component powder particles, it is likely that the dispersions coarsened during fabrication. Gregory and Goetzel, in their studies of extruded alloys of 80 pct Ni—-20 pct Cr matrixes with nonmetallic dispersion, observed a definite coarsening of the alumina dispersions in alloys sintered at 2280°F as cantrasted to those sintered at 2000oF. Similar observations on the spheroidization and growth of thoria particles finely dispersed in a nickel matrix were made by D. K. Worn and S. F. Marton.3 As a result of such coarsening, much of the effort expended in the preparation of very fine powder mixtures would be lost. The mechanical properties of the alloys which had experienced coarsening would be expected to be poorer than if the original dispersions had been retained. EXPERIMENTAL PROCEDURE Ni-Al2O3 alloys were produced from powder prepared by a coprecipitation technique. Aluminum hydroxide and nickel hydroxide were coprecipitated from chloride solutions of the metals. The mixed hydroxides were calcined to form metal oxides and the nickel oxide in the mixture was selectively reduced to nickel by treating it in hydrogen. Specimens were compacted from the resultant powder which consisted of a fine, uniform mixture of aluminum oxide and nickel particles. The compacts were sintered by resistance hot pressing4, a densification technique which requires exposure times of the order of only a second or less at elevated temperatures. A conventional sintering process was not used, since the temperature required for densification would have to be in the region in which the stability of the dispersion was to be studied. A series of hot pressed specimens were treated in hydrogen at temperatures from 2140o to 2470°F (1171o to 1355oC, for times up to 120 hr. Changes in the microstructures were studied by electron microscopy using the two-stage preshadowed carbon replica method.5 In performing a lineal analysis on a series of micrographs from each specimen it was found more convenient to determine the mean free path between alumina particles rather than particle radii as the parameter of growth. Although these quantities are directly proportional for only spherical particles, the alumina particles in these alloys

Jan 1, 1962

By C. G. Dunn, F. Lionetti

The energy associated with grain boundaries in polycrystalline aggregates is believed to play a major role in grain growth processes and, when growth ceases, to determine the final equilibrium grain boundary angles. Further, the energy of grain boundaries of recrystallization nuclei is a factor in nucleation processes. It is important to know, therefore, how the energy per unit area of a grain boundary, that is, the grain boundary surface tension y, depends on the difference in orientation of the two lattices of the grains producing the boundary. Although the problem is important, surprisingly little has been done toward a quantitative evaluation of the effect of orientation difference on grain boundary energies. C. S. Smith1 recently has discussed this problem and in addition to showing effects of orientation difference on equilibrium angles has shown a variety of interesting effects of surface tension on the appearance of microstructures. Fig 1 and the following relations expressed in Eq 1, which connect equilibrium grain boundary angles and surface tensions, illustrate equilibrium conditions which are believed to hold true in metals. ?l2 _ ?23 _ ?l3 [1] sin ?3 sin ?1 sin ?2 Clearly any two of these surface tensions can be expressed in terms of the third when the equilibrium angles ?1, ?2, and ?3 are known. Applied to the present problem for solid state equilibrium of three grains, the angles ?1,?2 and ?3 must be measured in a plane perpendicular to the line of junction of the three grains. Normally a direct determination of these angles from random microsections is impossible. Consequently Harker and Parker2 and Smith1 (except for some measurements on flat specimens) resorted to a statistical method to determine equilibrium grain boundary angles. Smith reported that grain boundaries meet the surface of a piece of metal nearly perpendicularly. He reported also, in connection with direct angle measurements on flat specimens with grains extending through the thickness, that angles varied appreciably from 120" and concluded that there was a measurable effect of orientation difference on surface tension. Another direct way of determining equilibrium angles and a method adaptable to studying particular configurations, recently suggested by Dunn,³ is to use a three-grain flat specimen with orientations of grains so chosen that the junction line of the three grains will be straight throughout the thickness and perpendicular to the surface of the specimen. Choice of orientations is possible when individual grains of each group can be grown to predetermined orientations through the reorienting and growth of " seed crystals " as described.³ Not only is it possible, for example, to have grains with the same crystallographic plane in the plane of the specimen, but a given orientation difference between two grains can be made a common factor to an unlimited number of three-grain groups while a series of orientation differences is investigated. Any effect of anisotropy of gas-solid surface tension due to grain orientation should be minimized by having all gains oriented the same with regard to crystallographic plane in the plane of the specimen. Another feature of the three-grain group is the notched grain boundaries as shown in Fig 2 for one specimen (S4). The notches serve to anchor the end positions of the grain boundaries (especially at high temperatures) while the central and junction point of the grains moves toward an equilibrium position. Final equilibrium should produce straight grain boundaries if the notches are very narrow and if changes in orientation* of the grain boundary do not alter the surface tension.† If one assumes the straight line condition and no change of surface tension with small changes in grain boundary orientation and finds the equilibrium configuration by a minimization of the grain boundary energy, one obtains the relations given in Eq 1. The approach to straight line boundaries or to minimum energy configurations in specimens containing large grains, such as those used in the present investigation, may be very slow compared with the approach to equilibrium conditions for the grain boundary angles. It may be desirable, as proved to be the case in the present investiga-

Jan 1, 1950

By R. G. Treuting

Germanium single crystals strained in tension at 600°C slip on the {Ill} plane and, macroscopically at least, in the <110> direction. Deformation is in homogeneous: various localized rotations are observed, as is a banding consistent with secondary slip banding. The structure after deformation is polygonized with a domain size of about 2x1O-3 cm. In relaxation tests, an incubation period prior to flow is observed, of duration inversely related to temperature and applied stress. Under continuous loading, there is a sharp first yield point. A critical resolved shear stress therefore must be cited with respect both to temperature and to rate of loading. At 600°C, when loading proceeds at 2900 psi per min, it is 1310 psi. The yield point phenomenon is suggestive of Cottrell&apos;s solute atom atmosphere theory and five points of qualitative agreement with this theory are found. PLASTICITY of germanium at elevated temperatures has been reported by Gallagher,&apos; who ascribed it to slip on {Ill) planes and described some associated effects. Preliminary experiments with single crystals of silicon and germanium loaded as simple beams confirmed {ill) as the slip plane of both materials.V his was demonstrated by the standard technique employing traces on two surfaces of known angle on a deformed crystal of known orientation.3 These experiments did not fix the slip direction, since more than one glide system operated. Uniaxial tensile straining is preferred for this purpose in order to restrict slip to one predominant system and to provide an unequivocal determination of the orientation change with respect to the stress axis. Experimental Method Specimens were diamond-sawed from germanium crystals containing about 5x10-5 wt pct Sb prepared by the zone-leveling process described by Pfann and Olsen;4 these specimens measured about 81/2 in. long, 0.20 in. wide, and were of various thicknesses from 0.035 to 0.060 in. Prior to testing, a specimen was coated over 1 in. or more of length at each end with Apiezon wax, chemically polished (in a solution of 15 ml HF, 25 ml HNO,, 15 ml CH3COOH, and 3 to 4 drops Br2), and dewaxed in warm xylene. A brief re-etching after scribing through a complete wax coating with vernier dividers provided gage marks at 0.200 in. intervals on the polished surface. A specimen with grips soft soldered to the ends was passed through the furnace tube and the grips pinned to the tensile machine in series with a stress gage. The Schopper testing machine is best described by reference to the illustration on p. 107 of Schmid and Boas5 and is operated with the pendulum arm locked, fixing the upper head. Load is applied through the screw-driven lower head, manually or by reduced speed motor. The furnace is 21/2 in. long surrounding a 4x7/16 in. ID quartz tube and was positioned about the specimen to permit free motion. The inert or reducing atmosphere required was sufficiently provided by a flow of helium introduced at the center of the furnace tube, with the tube ends loosely plugged with asbestos paper. Surface corrosion was slight. The stress gage employs a Be-Cu strip with SR-4 units incorporated in a simple bridge network with provision for balancing and calibrating. The bridge output on loading is fed through a Leeds and North-rup dc amplifier to a Speedomax 10 mv recorder, and calibration is obtained by dead loading. Experiments of two types have been conducted. Most have been in relaxation at constant elongation. One stress-strain curve has been taken with the machine continuously driven. Following extension of a specimen, Laue X-ray photographs were taken to obtain the orientation change between deformed and undeformed regions, recorded on a single film by translating the specimen in a plane normal to the beam between exposures. Sequences of such multiple exposures were made on some specimens to include the entire orientation range on one film. Slip Direction To obtain a maximum orientation change with a single slip system, crystals of very closely <110> axial orientation were used. The classic determination of slip direction rests on establishing that direc-

Jan 1, 1956

By H. C. Fiedler

The development of cube-on-edge secondary re crystallization texture in Si-Fe strip depends upon the ability of inclusions, such as manganese sulfide, to restrain nomal grain gvowth. The ability of inclusions to perform this function is shown to depend upon their size and distribution. The desired uniform dispersion of many small inclusions is obtained by controlling the cooling rate from above the solution tempmature of the inclusions or, alternatively, by drastic &apos;quenching from above the solution temperature followed by heat treating at a lower temperature. The development of the cube-on-edge secondary recrystallization texture in Si-Fe strip depends upon both establishing the proper primary recrystallization texture and having inclusions to restrain normal grain growth. It has been suggested that the first requirement is met with a texture which, though weak, is near (110)[001]. A mechanism for secondary recrystallization originally proposed by ielsen&apos; is consistent with the presence of this primary texture. It is visualized that a secondary grain appears where two adjacent grains happen to be sufficiently similar in orientation to be capable of behaving as a single large grain. This pair of grains will grow at the expense of its smaller neighbors as a consequence of its having lower grain boundary free energy. Other explanations of the origin of the secondary recrystallization texture have been offered,&apos; and it can be concluded that the mechanism is not fully understood. Nevertheless, it is apparent that operationally the necessary primary recrystallization texture is obtained simply by interposing an anneal during the cold reduction to final gage. The role of inclusions in the development of the secondary recrystallization texture has been demonstrated by May and Turnbull4 in a comparison of a high-purity heat and a heat containing manganese sulfide. They showed that the driving force for secondary recrystallization is inversely proportional to the diameter of the matrix grains and that the function of the inclusions is to maintain a small matrix grain size. Other inclusions, such as various sul- fides,&apos;)&apos; silicon nitride,8 and vanadium nitride,&apos; titanium carbide,&apos;&apos; and vanadium carbide," have been shown to be effective in promoting secondary recrystallization to the cube-on-edge texture. There is also evidence that silica inclusions in Si-Fe strip made by powder-metallurgy techniques perform this function.&apos; This report is concerned with the second of the two requirements for secondary recrystallization, namely the importance of the metallurgical control of the size and therefore number of inclusions. While the concepts involved are simple, they are fundamental to the making of this material. EXPERIMENTAL PROCEDURE A heat containing 3.27 pct Si, 0.026 pct S, 0.06 pct Mn, and 0.004 pct C was made in an air induction furnace from electrolytic iron, 98 pct ferro-silicon, electrolytic manganese, and iron sulfide. The heat was divided between graphite and baked-sand molds with a cavity 2-5/8 by 5 in. and with walls 2-3/4 in. thick. Slabs, 1 in. thick and 2-5/8 by 5 in., were cut from the ingots and hot-rolled either in the as-cast condition or after one of the heat treatments described later. After pickling, the 80- to 100-mil-thick hot-rolled band was, unless otherwise noted, heat-treated for 5 min at 900°C before being cold-rolled to 25 mils. After a heat treatment of 1 to 3 min at 860°C, the strip was cold-rolled to 12 mils, the final thickness. The percent cube-on-edge texture was determined by dividing the maximum torque as averaged from four samples by the maximum torque of a 3-1/4 pct Si-Fe single crystal having the (110) plane in the plane of the sample. The torque measurements were made in a field of 1000 oe on 1-in.-diam disks. RESULTS AND DISCUSSION The importance of the thermal history of the ingot is evident in Fig. 1 from the appearance of strips heat-treated in a temperature gradient. The sample

Jan 1, 1964

By P. R. Hines

Diphenyl guanidine is used as an accelerator in vulcanizing rubber. Other rubber accelerators are also flotation collectors, e.g., dithiocarbamate, thiazole, and the xanthates. Urea and its derivatives are good flotation collectors,&apos; and guanidine is the nitrogen analog of urea. These two characteristics suggested testing diphenyl guanidine as a flotation collector. Diphenyl guanidine has been tried in flotation work previously, but references give no details.&apos;.&apos; Bunker Hill Co. of Kellogg, Idaho, supplied the ore sample used in these tests. The sample was typical of the ore milled in 1949 and contained 4.52 pct Pb and 1.08 pct Zn. A flotation test made by the author with potassium ethyl xanthate as a collector, the same flotation reagents, and the same grind employed in regular Bunker Hill mill practice was the standard for comparing results with the compounds and derivatives of guanidine. The compounds and derivatives of guanidine are only fair collectors of galena. However, if potassium ethyl xanthate were used in the galena float, its presence later in the sphalerite float would make it impossible to introduce another type of collector and be certain which collector contributed the result, so the compound or derivative of guanidine under test was used in both the galena and sphalerite floats in Table I. On both the galena and the sphalerite in the Bunker Hill ore, the depressing action of sodium cyanide and zinc sulfate is much greater with collectors of the guanidine type than with the xanthates. If the depressing agents are left out when a guanidine type of collector is used, but a pH of 8.6 is maintained with either lime or sodium carbonate, the depressing action is approximately the same as in the standard xanthate test. Consequently the depressing agents, sodium cyanide and zinc, were not used in the galena floats of tests 1226, 1228, and 1286, Table I, so the galena floats would be on a comparable basis with the standard xanthate test. As shown by the tests in Table I, the loss in the tail when diphenyl guanidine is used is 8.3 to 9.3 pct, as compared to 17.6 pct with potassium ethyl xanthate, or a recovery of 2.3 to 2.0 lb more zinc. Concentrate grade is 13.7 pct with potassium ethyl xanthate and increases to 22.9 and 31.8 pct with diphenyl guanidine, showing a much higher selectivity. Unless the Barrett&apos;s No. 4 coal tar creosote is considered to be a collector, no collector other than diphenyl guanidine is present in the tests, Nos. 1226, 1228, and 1286. Tests 1218, 1253, and 1263 in Table I1 were run to check the effect of the depressing agents used in flotation of the galena (sodium cyanide and zinc sulfate) upon subsequent flotation of sphalerite by diphenyl guanidine. Urea was substituted for potassium ethyl xanthate in tests 1253 and 1263 because it is a good collector for galena and a poor one for sphalerite, and the effect of the depressing agents is more marked with urea than with potassium ethyl xanthate. Test 1205 checks the effect of urea alone without any depressing agents when used for the flotation of galena. Table I1 shows that diphenyl guanidine as a collector for sphalerite is compatible with other flotation reagents used in floating galena. When the depressing agents sodium cyanide and zinc sulfate are used in the galena flotation step, the amount of lime in the sphalerite flotation must be increased (compare 1253 and 1263). Table I11 gives some of the compounds of guanidine which were tested and compared. Some of the compounds and derivatives of guanidine* are solu- * Diphenyl guanidine is in commercial production and is available on the market. ble in water and others are not. Those tested were fed dry. When an organic collector is promising, its compounds and derivatives should be tested and their comparative collecting power recorded. Eventually, in this way, it may be possible to discover some of the essential chemical characteristics of a good collector. For example, it is interesting to compare the diphenyl and dibutyl derivatives in Table IV with those of urea in Table 111, Example 3, U. S. Patent 2,664,198. All are good collectors. Table I shows some of the effects of lime on recovery of sphalerite by diphenyl guanidine. Table V

Jan 1, 1960

By A. R. Troiano, A. B. Greninger

There is need for an adequate working hypothesis that would describe at least qualitatively the crystallographic mechanism for the transformation from austenite to martensite in steel. A general theory would not only be of great assistance in the correlation of existing data and in planning future experimentation, but would also form the basis for an eventual explanation of the property changes that accompany lattice transformations. The mechanism of martensite formation described in the following pages is the outcome of two new experimental determinations: (1) the accurate evaluation of the lattice relationship between austenite and individual crystals of martensite, and (2) the measurement and analysis of the change in position that a volume of austenite undergoes when it transforms into a crystal of martensite. For this latter study, the stereographic analysis of shear was employed; this method greatly simplifies the solution of lattice-shear problems, and some space is devoted to its description. Lattiice Relationships and Habits PREVIOUS WORK The lattice relationships between austenite and martensite in carbon steels have been studied by Kurdjurnow-and Sachs,&apos; and by Wassermann;2 and in iron-nickel alloys by Nishiyama.3 Wassermann,2 and Mehl and Derge.4 The studies by Kurdjumow and Sachs and by Wassermann were made on single (austenite) crystals of quenched 1.4 pct carbon steel, and the results of these two independent studies agree closely with the postulated lattice relationships: (III)r||(0ll)a [101]r [111]a [1] Both Nishiyama and Wassermann worked with an alloy of iron plus 30 pct nickel (all austenite at room temperature), and "martensitic alpha" was formed by cooling in liquid air. They agree that the lattice relationships for these conditions are: (lll)r||(011)a [112]r[011]a [2] Mehl and Derge worked with a range of iron-nickel alloy compositions centered about 30 pct nickel. They concluded that when the transformation takes place near room temperature or above, relationship [l] holds, but if the same specimen is made to transform at -195°C, relationship [2] obtains;intermediate temperatures evidently produced a combination of these two relationships. Sachs and co-worker~,1,7 as well as Nishiyama,3 have proposed transformation mechanisms for martensite formation.* Both of the mechanisms picture the transformation as initiated by shearing movements along the octahedral [Ill] plane of austenite, followed by suitable expansion and contraction to complete the transformation. These mechanisms have been described and commented upon by Mehl, Barrett, and Smith,8 Mehl and Derge,4 Wassermann,2 and others, and generally accepted by investigators in this field. Greninger and Troiano9 have recently published the results of a detailed study of the shapes and orientation habits of martensite crystals in plain-carbon and nickel steels. They found that, contrary to previous assumptions, martensite plates form not along the octahedral planes but along austenite planes of very high indices; these results were in line with those of previous studies of martensite reactions in nonferrous alloy systems by Greninger and coworkers.6,10 Greninger and Troiano concluded that the transformation theories of Kurdjumow and Sachsl and of Nishiyama3 are untenable. Phragmén11 reached a similar conclusion. EXPERlMENTAL METHODS The object of this particular study was the evaluation of (1) lattice relationship between austenite and martensite, and (2) relationship between the martensite lattice and the martensite plate. The technique used for solving these problems was similar to that used by Greninger6 on martensitic structures in 8 copper-aluminum alloys. Briefly, the method consists of grinding and polishing a specimen on a surface parallel to an individual martensite plate and thus exposing a single martensite crystal for an area of l to 3 mm. The orientation of this exposed martensite crystal is then determined by means of a back-reflection Laue X ray pattern.12 Another pattern is obtained from the matrix crystal, and a stereo-graphic plot of data from these two patterns then provides the solution to the problem. It is necessary to repeat this process on several crystals in order to determine whether or not the solution is unique.

Jan 1, 1950

By Jean-Jacques Prompsy, J. S. Rinehart

Some time ago a study was initiated at the Colorado School of Mines in an effort to arrive at a better understanding of the stress fields developed within drill bits under dynamic loading and the influence that these stress fields could have on the failure of the bits. Particular emphasis has been given to the influence that bit shape has on the establishment of highly localized, potentially destructive stress inhomogeneities within the bit. The study has been divided into three phases involving three velocity regimes: impacts at very low velocities, 0 to 20 ft/sec, a velocity range in which dynamic effects are just beginning to be found; impacts at velocities ranging from 20 to several hundred ft/sec, a range commonly encountered in practical drilling operations; and impulsive loading through the detonation of explosives, a region in which the dynamic effects are greatly exaggerated and made more identifiable. The ultimate objective is to provide basic data which will enable the mitigation through judicious design of the frequency and severity of these transient concentrations of intense stress, thereby prolonging and increasing drill efficiency. This paper presents results of the third phase of this study — the development of a better understanding of the dynamics and mechanics of failures caused by transient stress-wave interactions. The impulsive loading or transient waves in these experiments were generated by detonating small explosive charges placed on the ends of Plexiglas cylindrical rods terminating in truncated cones. Under such intense loading, dynamic effects are greatly exaggerated and, hence, made more identifiable. The explosion generates a high-intensity transient stress disturbance which moves through the rod, reflects from surfaces which lie in its path, and establishes momentarily narrow regions of high concentrations of stress where failure of fracture may occur. The peregrinations of these waves, their interactions and their effects have already been described in the literature (see, for example, Refs. 1 and 2). The locations and extent of the regions quite apparently are strongly dependent on specimen shape, making it possible through judicious shaping of specimens to relocate the highly stressed regions, minimize their extent, or eliminate them entirely. These experiments were designed, first, to identify more clearly the vulnerable regions in geometries relevant to drill-bit design and, then, to modify these regions in a predictable way by changing specimen shape. Through this latter process, it is anticipated that better bit design might evolve. The specimens used in the experiments were cylindrical rods, 1 1/2 and 1 1/8 in. in diameter, ended by a truncated cone, with the cone angles ranging from 45° to 130°. Upper cone face diameters were 1/2, 3/4, or 1 in. A small plastic-covered electric blasting cap detonated on the axis of the specimen produced the spherical shock wave. The detonators used were Olin Mathieson No. 6, which induced into the rod a transient saw-toothed stress disturbance of about 3-microseconds duration, corresponding to a wave length of 0.3 in. in the Plexiglas. Five distinct systems of fracture were observed: (1) along the axis of the rod, a lower system of fractures, the cracks focusing around one point for specimens having cone angles of 80° and 90° and, as the cone angle was increased, spreading downward; (2) just above these fractures, an upper system of fractures composed of horizontal cracks observable in some specimens but not of any appreciable extent; (3) a third system of axial cracks still above the latter, observable in the small cone-angle specimens; (4) in the upper part of the specimen, a system of radial fractures extending from the blasting point; and (5) circular spalling due to reflection of the wave on the boundary of the cylinder. Only the first three systems, the axial fractures, are examined here. LOWER TENSILE FRACTURE SYSTEM The first, lower system of tensile fractures, shown in the photograph of Fig. 1, was observed in almost all of the specimens. It was due to the reflected tensile wave coming in from the boundary of the cylinder as shown in Fig. 2. The reflected wave was cylindrically convergent and focused