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By W. A. Krivsky, R. Schumann

Relaxation calculations were made to find the temperature distribution in the refractory wall surrounding a tuyere pipe. One set of boundary conditions approxiwated those of a standard copper converter while a second set represented a hypothetical,thermally insulated tuyere pipe. The pvonounced cooling effect of the tuyere is related to the problem of tuyere accretions and tuyere bunching. PARTICULARLY severe service conditions are encountered in the tuyere zone of a basic copper converter during the matte blow. High-temperature gradients result from the juxtaposition of the hot charge and the tuyere pipe carrying cold air. Refractory temperatures near the tuyere mouth vary rapidly with time when the blast is turned on or off. One of the most serious problems is the formation of magnetite accretions around the tuyere mouth, which occurs very rapidly under some operating conditions. As a result, continual punching of the tuyeres is necessary to maintain a satisfactory rate of converting. Thus, if some means could be devised for keeping the tuyere pipes fully open without necessity for punching, a considerable saving should result from reduction in labor cost, maintenance of full capacity operation, and reduction in refractory costs. Recent quantitative studies of the FeO-Fe,O,-SiO, system1 have shown that the solubility of magnetite in iron-silicate slags decreases rapidly with de- creasing temperature in the range of copper converting temperatures. Data taken from the previous work are shown in Fig. 1. Thus the formation of "horns" and accretions around the tuyere mouth can result simply from the freezing out of magnetite on the cooler areas of refractory immediately adjacent to the tuyere pipes. One might expect to find a correlation between the severity of magnetite formation and the area of refractory surface which is cooled below the freezing point of the slag (corresponding to magnetite precipitation). Magnetite itself has a very high melting point (1597°C) so that the accretions are for all practical purposes infusible. The accretions might be dissolved by increasing the silica content of the slag and at the same time raising the temperature, but this approach is not feasible because it results in rapid corrosion of the basic refractory lining of the converter as a whole. In order to understand better the problems involved in tuyere design and operation, it seems essential to have at least a semiquantitative idea of the thermal conditions in the tuyere zone. Accordingly, this paper presents results of thermal calculations for an idealized copper converter tuyere. These calculations follow the so-called relaxation

Jan 1, 1960

By Arthur B. Cummins

Mineral fillers are employed in United States industries to the extent of more than seven million tons annually, valued in excess of a hundred million dollars. This substantial usage involves a wide variety of mineral materials. To this may be added products manufactured from minerals, such as carbon black, portland cement, lime or chemically precipitated calcium carbonates, which would add substantially to the total. The purposes for which fillers are used differ considerably. Minerals used as fillers are mostly silicates, silicas, and carbonates as referred to hereinafter. The term "mineral filler" has various meanings in mineral technology and in the arts. Fillers are comparatively inert and their action is mainly physical. Materials that are employed primarily for chemical reactivity, or for pigment or abrasive functions ordinarily would not be considered to be fillers when used for these purposes. Nearly all filler usages are based on advantages which are gained by desired modification of composition properties or by improvements in processing. A simple definition for a filler is an inert material that is included in a composition for some useful purpose. This definition may be amplified or made more specific for each of the filler usages, the major ones of which are: paints, paper, plastics, rubber, bituminous compositions, pesticides and fertilizers. There are in addition a whole host of minor usages. Powdered minerals when employed as components in paints, varnishes and lacquers are considered as extender pigments or low refractive index pigments. In paper, the term loading material as well as filler is used; in pesticides, the terms diluents and carriers connote different functions. For bituminous compositions, rubber and plastics, the usage of the simple word "filler" is more usual, but the designation loading material is sometimes used. Minerals Used as Fillers Most of the industrial minerals, and many rock powders are employed to some extent for different filler uses. These usages vary from year to year depending on availabilities, costs, technologic trends and advancements. For the major applications, however, and for the more particular requirements at any given period, there are general trends which favor a more or less restricted group of filler products for each of the major consumer fields. This selection of materials is determined by the characteristics of the individual filler products, their effectiveness in fulfilling the primary function or functions for which they may be employed, and the cost after incorporation in the finished product. The mineral-bearing materials of major importance as fillers are: limestones, clays of several types, talc, pyrophyllite, mica, barite, diatomite, crystalline silicas, asbestos, slate and other rock dusts. Others of secondary importance include: gypsum, vermiculite, phosphate rock, perlite, and pulverized wastes, such as slag and fly ash. A considerable number of other minerals are used to lesser extent. Among these minor mineral materials are: feldspar, pumicite, wollastonite,18 tripoli, nepheline syenite,6 coal, altered volcanic rock and others.2 Indeed, most mineral materials, when reduced to fine particle size may have some potential usage as fillers, depending on their properties, availability and price. On the other hand, the more exacting filler requirements

Jan 1, 1960

By Ward C. Smith

The industry of producing and processing boron compounds is called the borax industry because the chief product is borax, the decahydrate of disodium tetraborate. For the same reason, it is common to speak of borax mining. Reference to borate mining also is common, and while appropriate where it emphasizes the diversity of borate minerals that are mined in various countries, it is rather unsatisfactory where used in a general sense, because it seems to exclude the important production of borax from brine at Searles Lake, California, and of boric acid from steam vents in Tuscany, Italy. The terms "boron industry" and "boron mining" might seem more comprehensive, but are little used, and this is fortunate because they would be misleading-the element boron is manufactured only in small amounts for special uses, and it is not found free in nature. In most occurrences, boron is combined with oxygen and is in a borate or borosilicate material. The history of the modem borax industry starts with the introduction into Europe of borax from Tibet in the 13th century, about the time of Marco Polo, if not actually by him. The discovery that borax has unique value as a flux in metal soldering and ceramic glazing must have been made at some unknown time much earlier. As a rule, any mineral that has been used so long that its early history is lost must occur in deposits that are easily recognized and worked, and this is undoubtedly true of borax in Tibet. According to meager accounts,9 the borax occurs there in arid mountain basins as surficial crusts that coat the ground about thermal springs and seeps of mineralized water, and as coarser crystals in the bottom muds of shallow pools and lakes. Much the same essential features of surface exposures and minerals easy to recognize and recover characterize most of the deposits later found and worked elsewhere. The borax industry at the present time is faced with rising demands for its products, and consequently is increasing its productive capacity and appraising its borate resources.18 The areas that contain the known borate deposits are most likely to yield additional production, hence their distribution in the world is of interest, and is summarized later in this chapter. Mineralogy The mineral raw materials used by the borax industry include various borates mined in several countries, borax extracted from brines at Searles Lake in California, and boric acid extracted from the steam of vents in Tuscany in Italy. The hydrated borates[$] of chief commercial importance are listed in Table 1, which also shows their chemical composition. The properties of only the four most important borates are summarized here, but detailed descriptions of the borates and the minerals commonly found with them can be found in mineralogy textbooks.41 Ulexite generally forms clusters of silky fibers rather than large individual crystals. A

Jan 1, 1960

By H. Conrad Meyer

The wizardry of nucleonics has added new and greater dimensions to the almost inseparable "twins"-zirconium and hafnium. So close is their relationship that neither element is found free of the other in any presently known mineral. Although zirconium in the form of its oxide was discovered in 1789 by Klaproth, the metal in an impure, nonductile form was not isolated until 1824 by Berzelius. About 100 years later -1925-van Arkel and deBoer developed and patented a technique for the deposition in vacuo of crystalline, coherent, highly ductile metal of extreme purity on an electrically heated filament through the dissociation of gaseous zirconium tetraiodide. Within the past five years both zirconium and hafnium have been dramatized by the press and in popular science magazines. This has led to the false assumption that practically all of the world consumption of zirconium ores is used in the production of the metals. Recent statistics on the subject show that not over 15 pct of the zirconium ore consumed in 1958 went to ferrosilicon zirconium and zirconium metal. The rest was consumed in refractories, foundry sand and facings and ceramics. The importance of zirconium as a component in compact, relatively lightweight nuclear energy units, such as those now used in the submarine Nautilus,6 is well established. A rival of zirconium metal as a casing for atomic fuels is a newly developed ceramic body. It is claimed to be cheaper than zirconium-to withstand higher temperatures-and to be more resistant to corrosion. Whether such ceramic casings have the required low thermal neutron absorption cross section, high strength and easy formability of zirconium is yet to be demonstrated. Hafnium, because of its low order of abundance and its close chemical relationship to zirconium, was not definitely recognized as a new element until around 1923, despite prior claims. A study of the X-ray spectra of zirconium led to its identification. The circumstances leading to the discovery of hafnium were much less fortuitous than those surrounding zirconium. The more precise tools of arc and X-ray spectrometry lent themselves admirably to the search for elements to fill certain gaps in the periodic table. [ ] Pure, ductile hafnium-a metal similar in appearance to stainless steel-has a specific gravity of 13.3 (zirconium 6.52) and a melting point of 2,200°C. In other respects it closely resembles zirconium except in one important respect which gives it a preeminent position in nuclear energy development, namely, a high thermal-neutron absorption cross section. This explains the necessity of hafnium-free zirconium in atomic piles. The ability of hafnium to capture thermal neutrons makes it an excellent "moderator" of "governor" when used as control rods in nuclear reactors (Table 1).

Jan 1, 1960

By W. E. Horst

John Dasher (Central Research Laboratory, Crucible Steel Co. of America, Pittsburgh. Pa.)— Getting spodumene to float quickly and cleanly can be a problem. The author has presented an excellent account of a valid and useful approach to the scale-up of such problem floats. This indicated advantages for doubling retention time, i.e., buying another set of flotation cells. The author states that 21 pct of the spodumene floated in 2 min in the laboratory cell, that the grade of the rougher was about 75 pct spodumene, and that the final tailing contained 4 to 12 pct spodumene in different sizes with the present cells and 1 to 9 pct spodumene with twice as many cells. About 20 years ago, this writer obtained in the laboratory the flotation of over 90 pct of this spodumene in a King's Mountain sample in 1 min at a grade of 90 pct spodumene in the rougher and a final tailing that contained only 1 pct spodumene. The methods of Norman, Ralston," and Gieseke' were used, which teach that spodumene floats quickly and cleanly if its surfaces have been properly conditioned chemically and/or mechanically prior to flotation. Although feed preparation is not discussed, the results reported indicate that it is inadequate. This writer suggests that improvements in this area might be more effective than doubling the number of cells. W. E. Horst (author's reply)—Dasher's comments are appreciated by the author and require some clarification. He suggests that improved spodumene flotation performance may be obtained by feed preparation techniques rather than increased retention time in flotation. Certainly flotation performance is dependent on feed preparation and this is an important feature in the flotation process. It is true that certain types of spodumene ores, particularly weathered ores, require more complicated feed preparation processing than clean ores to achieve the desired flotation results. It was not implied that current feed preparation techniques are the same as experienced during the scale-up investigations. Although discussion of feed preparation was omitted from the article on scale-up relationships, the important feature was that pre-treatment processing was the same for each level of operation investigated— laboratory, pilot plant, and plant scale. Under these similar conditions large differences existed in recovery for comparable time intervals in each scale of operation. It is highly probable that feed preparation techniques could be modified and thereby increase the flotation rate for each scale or all scales of operation discussed. However, modifications would have to be justified on an economic basis.

Jan 1, 1960

By N. A. Richard, A. E. Austin, R. E. Maringer

AS part of a detailed study of the structure of metallic meteorites, the concentration and distribution of iron and nickel in the various phases of meteor -itic iron have been measured using an electron-probe microanalyzer. The specimen used was cut from a position about 3 in. below the surface of the Grant meteorite, a one-half-ton iron specimen (containing 9.35 pct Ni) found in New Mexico some years ago. A photomicrograph showing the general Widmanstztten structure, somewhat typical of iron meteorites, is shown in Fig. 1. The line across which the analyses were made is indicated by arrows. This area was chosen so as to evaluate the iron-nickel concentration in the three principal phases visible in Fig. 1. These phases, in the language of meteoritics, are kamacite, taenite, and plessite. Kamacite is the a-

Jan 1, 1960

By R. J. Borg, C. E. Birchenall

Vapor pressures of eight compositions of Mg-Cd have been determined by the Knudsen effusion technique. Measurements are made at several temperatures for each alloy and the results interpolated to a common temperature for the calculation of the activities. It is not possible to obtain values for the partial molar enthalpies because of the narrow temperature range spanned by the measurements. The results show less precision than those obtained for pure Cd which are also reborted. These alloys are extremely susceptible to corrosion which provides a possible explanation for the lack of precision. Nevertheless, the values of the activity are in good agreement with the results of electromotive force measurements previously reported for the Mg-Cd system. MAGNESIUM and cadmium are mutually soluble in all proportions in the solid state and form a single phase which has the hexagonal close-packed structure. X-ray investigations of this system1,2 have revealed a rapid variation in the relative dimensions of the unit cell occurring at approximately 50 at. pct. The rate of change of the c/a ratio with composition increases markedly for alloys containing more than 50 at. pct Cd. The purpose of this investigation was to determine the activity of Cd in the neighborhood of 50 at. pct and to discover whether or not the thermo-dynamic properties undergo a similar rapid change. The activities are calculated from vapor pressure data obtained by the Knudsen effusion method. Unfortunately the precision of the data from which the thermodynamic values are calculated is insufficient to establish unequivocally a departure from the normal trend. The results are reported primarily because they substantiate the only previously reported activity measurements3 and because they include values for pure Cd which in contrast to those of the alloys show excellent precision. The Cd-Mg system is known to contain several ordered phases. However, this investigation was made at temperatures considerably above the transition temperatures, and the alloys may be regarded as nearly random solid solutions. EXPERIMENTAL Apparatus—The effusion cells are machined from solid tantalum rod. The lids consist of threaded, flanged rings of tantalum onto which are welded shallow cups of 4 mil molybdenum foil. The orifice, which is located at its center, is made by grinding off a small dimple produced with a sharpened punch. Such an orifice has been mounted in plastic, sectioned, and the thickness of the orifice edge measured in a microscope. The maximum thickness is 0.00016 in., and the Clausing factor is consequently equated to unity. The area of the orifice is determined by tracing its projection on the screen of the metallograph at a known magnification and measuring the area of the tracing with a planimeter. Excellent temperature control is achieved with a 4 by 18-in. alundum core, gradient-wound, furnace

Jan 1, 1960

The Rosebery and Hercules mines, situated in the Rosebery-Williamsford district in western Tasmania, have a history of production dating back to 1896-7, although full scale production did not commence until 1936, following the development of a satisfactory process of selective flotation (Hall, Cottle, Rosenhain and McGhie, 1953). The mineral composition of the Rosebery zinc-lead ores was first described in detail by Stillwell (1934). The Hercules ore is generally similar, but as yet no descriptions of it have beenpublished.Since Dr. Stillwell's paper appeared, the management of the Rosebery and Hercules mines has from time to time submitted a number of interesting mineral specimens to C.S.I.R.O. Mineragraphie Investigations. Examination of these specimens brought to light eight minerals, some relatively uncommon, not previously recognized in these ores.They are cassiterite, molybdenite, stannite, electrum, meneghinite, boulangerite, pyrargyrite and pyrrhotite. Some of the specimens are also rich in tetrahedrite and gold. In addition each of the other ore minerals described by Stillwell, viz. pyrite, sphalerite, galena, bournonite, chaleopyrite and arsenopyrite, was detected in one or more of the specimens examined during the present study. The principal gangue minerals were found to be quartz, manganiferous carbonate, sericite and barite, agreeing closely with the observations of Stillwell.The present study was based on the examination of the following eight specimens.

Jan 1, 1960

By W. H. Ode

Because trade increased among various nations after World War II, the Coal Committee of the Economic Commission for Europe established a Classification Working Party in 1949 to develop an International system for classifying coal. Although national classification systems existed, they had been developed in accordance with characteristics of domestic coals without reference to coals of other countries. Terms for describing similar or identical coals differed in each nation. This caused confusion in evaluating coals shipped in international trade and also hampered exchange of technical information on problems of coal utilization. Experts4/ participating in the classification project early in their work agreed that two systems should be formulated, one for the higher rank coals or so-called "hard" coals in European terminology and the other one for the lower rank coals, the latter designated mainly as brown coals and lignites in the various countries. Rank refers to the degree of metamorphism (progressive alteration) in the natural coalification series from lignite and brown coal to anthracite. The system for classification of hard coals was published late in 1956 as a document of the United Nations.5/ Results of a study for applying this system to American coals were published in 1958.6/

Jan 1, 1960

By B. S. Crocker

Pebble grinding was used at Lake Shore Mines in 1949. A full description of experimental evidence and test plant results was published in 1952 1 and further operating details in 1954 2.' In more recent years the term autogenous grinding has been coined and is now frequently seen in the technical literature. Autogenous crushing and/or grinding covers any grinding mill in which the larger pieces of ore are made to grind the fine pieces; the crushing and grinding may be either dry or wet. This discussion deals only with wet autogenous grinding, and only in the fine grinding part of the circuit, i.e., from 6 mesh to 92 pct —325 mesh. The term pebble milling could apply to fine autogenous grinding in which the pebbles are made from the ore itself, or it could also refer to grinding with pebbles, such as flint pebbles, from a source outside the mine. The first mill to use screened ore to grind the ore (1949) was Lake Shore Mines, Kirkland Lake, Ont. Pebbles were screened from the jaw crusher discharge and used in 5x16-ft tube mills which had been converted to 6 ft 8 in. by 16-ft grate discharge pebble mills. The same general practice was adopted the following year by the Wright-Har-greaves Mine in Kirkland Lake. Shortly after that the Neptune Mines in Nicaragua started correspondence with the writer concerning the possibility of using screened ore for grinding in their plant. They first ran some plant-scale tests which confirmed the Lake Shore findings, with the ultimate result that their plant was successfully converted in 1956 to an autogenous grinding plant. In 1957-1958 the writer was successful in converting the grinding plant of Renabie Mines in northern Ontario to autogenous grinding. In all these plants the existing grinding equipment was converted, usually by expanding the diameter of the shell to make the change from steel grinding to ore pebble grinding mills. In all the above plants primary grinding was done in either small rod mills or ball mills. These mills first reduced the pebble mill feed to about 6 mesh. The final grinding in the pebble mills varied from 75 pct —200 mesh to 92 pct —325 mesh. At Lake Shore three stages of pebble milling were used, with a different size pebble in each stage. In other parts of the world interest was being shown in this form of grinding, and in March 1952 the writer had some correspondence with the mill staff at Outokumpu in Finland, with regard to the pebble system used at Lake Shore. At Stockholm in 1957 the account of the crushing and grinding system at Outokumpu was presented in a paper by H. Tanner and T. Heikkinen.V his is the only ore grinding plant that does not use grate discharges on its pebble mills; trunnion discharges equipped with heavy reverse spirals retain the pebble load. The first new mill designed to use screened ore as a grinding medium was the Bicroft mill at Bancroft, Ont., which began operation in the fall of 1956. In 1957 this plant was followed by similar installations at Faraday Mines, also in the Bancroft area, and the North Rankin Nickel Mines in the North West Territories. In 1958 the Dyno Mill at Bancroft was converted, using the same type of grinding. Since all these plants, designed by Kilborn Engineering (1954) Ltd., were originally planned as pebble grinding mills, they were able to take full advantage of the latest design and technique. They are neat in appearance and very efficient and easy to operate. Effect of Ore Hardness: It is often commented that this type of autogenous grinding applies only to hard siliceous ores. Experience has shown that this is not so. In the past ten years the author has had an opportunity to test more than a dozen ores, several of which were quite soft. One of these was shale. The softer ores actually make better looking pebbles than the hard ores. These soft ores produced no particles in the intermediate size range which could not be ground by the largest pebbles in the mill charge. Slabby ores, such as shales, make a suitable pebble for the —6 mesh grinding. It is not generally recognized that for fine grinding a spherical medium is not essential or more efficient. Another frequent objection to pebble grinding is the belief held by some operators that there is too much variation in the hardness of their particular ore to make it acceptable as a source of pebble media. Experience has also shown that this is not a serious problem at all. The variation in pebble load due to changes in the ore hardness is nothing like as great as most people would expect, and the method used for feeding the ore and controlling the the load in the mills is more than sufficient to take care of daily variations in ore hardness. This point

Jan 1, 1960

By A. G. Guy

Zinc vapor from a reservoir of liquid zinc maintained at lower temperatures was diffused into sets of copper-zinc alloys at 759° and 870° C and into sets of silver-zinc alloys at 650° and 700° C. Each set of ,four copper-zinc alloys consisted of pure copper and 90/10, 80/20, and 70/30 brass. Similarly the set of silver-base alloys consisted of specimens containing 0, 7, 15, and 20 pct Zn. Natural markers at the initial surfaces of the specimens ware "trapped" under a thin electroplate and their depth of burying was measured after diffusion. The ratio of diffusivities of the two components determined from these data and the chemical diffusion coefficient calculated by the Matano method agreed with previously reported results. The line of markers was irregular and was often discontinuous when a grain boundary was crossed. TECHNIQUES involving the vapor phase have been widely employed in studying diffusion phenomena in metals. Many investigators have evaporated the more volatile component from an alloy, but it is generally believed that the porosity created under these conditions interferes with adequate interpretation of the experimental results. The extensive work of Gertsriken6 has been criticized on this score. Accary1 found that the diffusion coefficient for de-zincification of brass is larger by a factor of five than that for zincification, although he attributed the difference to a higher vacancy concentration under conditions of dezincification. Balluffi and siegle2 thoroughly investigated the technique of adding a more volatile component to a less volatile base metal as a means for studying diffusion. They verified that no porosity forms in a brass under these conditions and that the diffusivities of the two components can be determined from observations of the motion of markers originally placed on the surface of the specimen. The mathematical analysis that they developed for treating the experimental data was modified in a later note, but essentially it involved using the graphical Boltzmann-Matano method that is customarily applied to solid-solid diffusion couples. The experimental method used in the present research was similar to that employed by Balluffi and Siegle except for two modifications. Balluffi and Siegle used alloy chips as the source of metal vapor. This procedure has the disadvantage that the concentration of solute at the surface of the specimen changes during the diffusion experiment as the alloy content of the chips is gradually decreased. This disadvantage was overcome by employing liquid zinc as the source of zinc vapor in a manner similar to that described by Herasymenko.9 There was then no limitation on the amount of solute usefully available, and several relatively large specimens could be diffused in a given experiment. The second modification was the use of natural markers on the surface of the specimen rather than larger, artificial markers, such as the alumina powder employed by Balluffi and Siegle. It was expected that the fine, natural markers would permit more precise measurement of the buried interface as in the case of ordinary sandwich specimens.10 EXPERIMENTAL The experiments were designed so that zinc from the vapor phase would maintain a constant zinc content at the surface of pure copper (or silver) and

Jan 1, 1960

By J. M. Ohm, C. M. Bunker

Two special tools for recovering gamma-ray probes and logging cable from drillholes have been designed by Ohm and Bunker and constructed by Ohm. Though intended specifically for U. S. Geological Survey equipment, they may be used with other equipment of the same general type. Fishing Tool for Probes: A fishing tool of the overshot type (Fig. 1) was designed to retrieve logging probes (sondes) that become disconnected from the logging cable and are trapped in the drillhole. When the tool slides over the top of the gamma-ray probe, studs on the bottom engage the shoulder near the top of the probe (Fig. 2), which is then pulled to surface. The barrel can be constructed from brass or steel tubing. Wall thickness is not a critical dimension, but the tool should be heavy enough to sink through mud or water in the drillhole. The internal length of the tool must be enough to prevent interference with the upper end of the probe head as the tool slides over it. The design of the probe head used by the USGS required a minimum free space of 2 1/2 in. inside the fishing tool, which was made 7 1/2 in. long to increase the weight. The lower end, which engages the shoulder of the upper end of the probe, contains three studs placed at 120" around the circumference of the tool and held in the engaging position by the tension of a spring wire. The studs can be made of any metal, such as steel, having high tensile strength. As the tool slides over the probe the studs are pushed outward from the center against the spring tension, allowing the tool to slide into position below the shoulder of the probe head. The spring tension forces the studs inward into the engaged position after they pass the shoulder. When the tool is raised the studs stop against the shoulder, preventing the tool from sliding up over the top of the probe. Once it engages the shoulder of the probe it cannot be freed until both probe and fishing equipment are recovered from the drillhole.

Jan 1, 1960

By J. H., R. W. Guard, Westbrook

In 1953 Kornilov and Mints' presented data on thermal expansion and electrical conductivity of the compound Ni3A1 which indicated the possibility of a transformation in Ni3A1 at about 600°C. The present paper gives results of some observations

Jan 1, 1960

By S. H. Moll, R. E. Ogilvie

The investigation of solid-state diffusion phenomena may lead to much information concerning binary alloys. In particular, a study of the concentration gradients present in multiphase diffusion couples can lead to the determination of the solubility limits of the single-phase fields in the phase diagram. The specific concentration gradient which results from the heat treatment of a diffusion couple depends not only upon the time and temperature of diffusion, but also upon the number of phases existing in equilibrium at the diffusion temperature. Such concentration gradients possess sharp discontinuities whose terminal points correspond to the solubilities existing at the limits of the two-phase field in the phase diagram at the diffusion temperature. In general, there will be a discontinuity in the concentration curve for each two-phase field which exists in the phase diagram between the concentration limits of the couple. A number of investigators have analyzed the gradients present in multiphase diffusion couples. 1-8 The iron-titanium phase diagram exhibits a y loop in the temperature range from 900" to 1400°C, and the limit of the a + y field lies at some composition which is less than 1 wt pct Ti for any temperature. It was felt that a diffusion study could yield values not only for the diffusion coefficients involved, but also for the chemical solubilities in the phase diagram. The concentration gradients were analyzed by an X-ray absorption technique developed by Ogilvie.6 The absorption of a monochromatic X-ray beam is measured in steps parallel to the diffusion direction and the resulting intensity gradients are transformed into concentration gradients by applying the laws of X-ray absorption in a binary system. This technique has been applied by ogilvie6 to the systems Ni-Au, Cu-Au, Fe-Cr, and Ni-Cr; by Gelles7 to the systems Be-Fe, and Be-Ni and by Hilliarde to the system Al-Zn. Linear X-Ray Absorption Analysis—The use of X-ray absorption analysis as a tool for determining concentration gradients arises from the fact that the beam is absorbed according to the quantity and species of elements present in the sample and not according to their state of aggregation. This method is more advantageous than the chemical analysis of machined layers since it is less time consuming and less expensive and can analyze a very small area. IF a homogeneous binary alloy (A + B) is analyzed with two different monochromatic X-ray beams I0(2) and lo(2) the following relation between the transmitted intensities, the intrinsic absorption coefficients of A and B for the two different radiations and the weight fraction of each element may be derived.' In (I/Io) (a+b) xa(u/p)a(2) + xb(u/p)8(2) Eq. [1] is independent of specimen thickness and density, but requires that either element A or B possess an absorption edge between the wavelength limits of the two monochromatic beams. I, is evaluated for each radiation by measuring the transmitted intensity through a varying number of foils of a suitable absorber. A plot of the natural logarithm of the transmitted intensity as a function of the number of foils, when extrapolated to zero foils, yields the value of I,. If a plot of the ratio in Eq. [ I] is calculated as a function of xA, then a master curve results. From

Jan 1, 1960

By W. C. Hagel, H. J. Beattie

Variations in the secondary phase reactions of six nickel-and cobalt-base alloys were determined as a function of solu-tioning from 1700" to 2200°F and aging at 1200" to 1800° F for times up to 1000 hr. Room-temperature impact energies and hardnesses were also measured. Precipitation hardening of these alloys results mainly from the grain-interior formation of ? '; M23C6 appears principally as grazn-boundary cells which can be eliminated by intermediate high-temperature aging treatments. Cellular precipitation of ?' occurs up to 1500°F in cobalt-nickel alloys devoid of chromium, where precipitation by this mode can be attributed to a large degree of lattice disvegistery. THE usefulness of nickel- and cobalt-base alloys is dependent on balancing the strength and ductility provided by the solid-solution matrix, dislocation-type subboundaries, grain-boundary phases and genera1 precipitation within individual grains. Since equilibrium relationships for complex austenitic alloys are not easily fixed, a satisfactory balance

Jan 1, 1960

By A. R. Troiano, E. A. Steigerwald, F. W. Schaller

The kinetics of crack propagation in a hydrogenated high-strength steel at subzero temperatures indicated that cracking progressed in a discontinuous fashion. The delayed failure process thus involves a series of crack initiations rather than the continuous growth of a single crack. The incubation time required for the initiation of delayed failure was controlled by the diffusion of hydrogen. The activation energy for the process was 9120 cal per g-alom. As the test temperature was lowered the incubation time constituted a greater percentage of the total tinze to fracture, and al -50°F the incubation and fracture times were essentially coincident resulting in instantaneous, catastroplzic fracture. A unique feature of hydrogen embrittlement is the delayed failure process in which the material fails under the action of a sustained load even though it is capable of supporting a higher load for a finite period of time.')' Delayed failure of steel and titanium is characterized by an incubation time, preceding the initiation of a crack in a highly localized region, and the subsequent growth of the crack to ultimate failure.3-5 The kinetics of crack growth in hydro-genated high-strength steels have been studied through the use of resistance measurements and have an important bearing on the mechanism of delayed failure. Delayed failure is believed to be merely a facet of hydrogen embrittlement in which sufficient time is allowed during a test for hydrogen diffusion. The current theories employed to explain hydrogen em-brittlement can be grouped into two types. one6-8 explains the embrittlement on the basis of the pressure exerted by molecular hdrogen in lattice voids or defects while the other9-10 attributes the embrittlement to the influence of hydrogen in the lattice. The mechanism used to explain the nature of the crack kinetics in delayed failure is based on the stress-induced diffusion of hydrogen to the area of maximum triaxiality.3 When the hydrogen concentration in this region reaches a critical value, a crack is nucleated. This initial crack propagates instantaneously until stopped by the higher fracture stress of the adjacent material of lower hydrogen content. The continuation of cracking must then await the further diffusion of hydrogen to the new region of triaxiality near the base of the crack where another initiation will occur. From this mechanism it follows that crack propagation is nothing more or less than a series of initiations with limited fracture. The purpose of this investigation was to examine the kinetics of crack growth in an effort to determine whether or not the process was discontinuous. Studies of crack propagation were conducted at low temperatures to retard the diffusion of hydrogen which is presumed to be the rate controlling process in delayed failure. MATERIALS AND PROCEDURE Specimen Preparation—A commercial heat of air-craft quality SAE-AISI 4340 steel, designated as Heat G, was furnished by the Republic Steel Co. in the form of %-in. hot-rolled bars. The material had the following chemical analysis: Composition of 4340 Steel—G Heat C Mn Si Ni Cr Mo 0,395pct 0.82pct 0.29pct 1.76pct 0.85pct 0.25pct Notched tensile specimens with less than a 0.001 in. radius, Fig. 1, were used throughout the investigation. The specimens were heat treated to a 230,000 psi strength level according to the following sequence: a) Normalize bar stock at 1650°F for 1 hr, b) Stress relieve at 1200°F for 4 hr and furnace cool,

Jan 1, 1960

By R. W. Fountain, M. Korchynsky

The precipitation phenomena occurring in cobalt-tantalum alloys have been investigated in the temperature range frm 500" to 1050°C by correlating the results of metallographic, X-ray, micro-and macrohardness, and electrical resistivity studies. The property andmacrohardness,changes were found to depend on 1) general precipitation, and 2) lamellar precipitation. Two new intermetallic phases have been identified: 1) a Co3Ta, a metastable ordered face-centered-cubic compound, and 2) a stable ß Co3Ta phase of hexagonal structure. In addition, the previously reported Co2Ta phase was found to exist in two allotropic modifications: the hexagonal MgZn,-type and the cubic MgCu2-type Laves phases. SINCE a large variety of structures can result as a consequence of the decomposition of a solid solution, predictions on the nature of property changes are difficult, if not impossible, to make. For any rational attempt to correlate properties and structures of a precipitation-hardenable alloy, a detailed understanding of the kinetics of decomposition and morphology of phase separation, as well as knowledge of phase relationships, appears to be prerequisite. Information of this type has been accumulated in the past for many alloy systems, both of theoretical and pastforpractical importance.1,2 Although the presence of intermetallic compounds has been reported in cobalt-base alloys,3 the amount of published information on precipitation-hardenable cobalt-base systems is very limited. A survey of the binary phase diagrams of cobalt indicates that cobalt-tantalum alloys might be of interest as typical of other cobalt-base systems in which Laves phases of the A,B type can be precipitated from solid solution. The present work has been undertaken, therefore, to study the kinetics and morphology of the precipitation reaction in this system and to establish a base for a correlation between the structural aspects and properties in this class of alloys. PREVIOUS WORK The only available phase diagram of the cobalt-tantalum system is based on the work of Koster and Mulfinger. According to these authors, the maximum solubility of tantalum in cobalt is about 13 pct (at 1275°C) and. less than 7 pct at room temperature. Tantalum additions lower the temperature of allotropic transformation of cobalt (about 420°C), and at 7 pct Ta, the high-temperature face-centered-cubic modification (ß cobalt) is retained at room temperature. The precipitating phase was originally designated as Co5Ta2 compound (55.2 pct Ta, about 1550°C melting point), but subsequent investigations by wallbaum5" identified this constituent as the A,B-type Laves phase. Wallbaum's data indicate that there are two modifications of this intermetallic compound: one richer in cobalt (Co2.2 Tao.8)of the hexagonal MgNi, type; and another of a higher tantalum content (Co2Ta) of the cubic MgCu, type. On the other hand, Elliott7 found that the cobalt-rich alloy (CO2.10,Tao.~l) was predominantly the cubic MgCu, type at 800°C and a mixture of both the MgCu2 and the hexagonal MgZn,-type Laves phases at 1000°C. At 1200°C, Elliott found only the MgZn, type while at 1400°C, he observed only the MgCu2 type. At the stoichiometric composition, Co2Ta, Elliott reported only the cubic MgCu2-type Laves phase in the temperature range of 600oto 1600°C. The precipitation of the cobalt-tantalum intermetallic compound is accompanied by a marked increase in hardness. According to Koster's4 data, the Brinell hardness of an 8 pct Ta-Co alloy increases from 230 to 340 upon short-time aging at 800°C. EXPERIMENTAL PROCEDURE The binary cobalt-tantalum alloys investigated contained 5, 10, and 15 pct Ta. The range of tantalum additions was thus slightly broader than the reported minimum and maximum solid solubility limits of tantalum in cobalt (7 and 13 pct, respectively)4 The alloys were vacuum-induction melted in a magnesia crucible using cobalt rondelles and technically pure tantalum sheet as raw materials. Deoxidation of the melt was accomplished with carbon, and the chemical analysis of the alloys is given in Table I. The effect of isothermal aging treatments on the progress of precipitation was studied on samples cut from cast ingots. These samples were solution treated for 2 hr at 1250°C and water-quenched. Aging was conducted in the temperature range from 500" to 1050°C for periods between 15 min and 1000 hr and followed by water-quenching. To prevent contamination from the atmosphere, all samples were sealed in evacuated Vycor or quartz tubes for heat-treatments. For solution treatment, argon at 0.2 atmospheric pressure was introduced prior to sealing of the capsule to prevent collapse at high temperature, and titanium sponge was placed at one end of the capsule to act as a getter. MACROHARDNESS The effect of aging on Vickers hardness (Dph) of

Jan 1, 1960

By Richard H. Jahns

Terminology and Basic Specifications Minerals and closely allied natural substances that are used for personal adornment, as raw stock for the fashioning of ornamental objects, or for other decorative purposes can be referred to collectively as gem materials. Industrial gem materials are those employed directly in various areas of industry. Substances that are manufactured for gem or industrial uses are termed synthetic gem materials; most of these correspond in composition and crystal structure to certain minerals found in nature. Imitation materials are those whose use is based upon their resemblance to substances of different composition and greater value. Gem stone is a designation commonly restricted to those materials suitable for personal adornment, and the complementary term ornamental stone is applied to the remaining materials not used industrially. This distinction is arbitrary and somewhat inconstant, owing to numerous geographic differences and historical shifts in end uses. Further, there is a complete gradation between the category of ornamental stones and that of dimension stone. Although many building and monumental stones are undeniably ornamental in their uses, treatment of such material is beyond the scope of this chapter. Substances that lose their identity in use are excluded from the gem category. Thus a transparent crystal of beryl would not be classed as a gem stone if it were treated as a source of beryllium metal. The adjectives precious and semiprecious have been employed as a means of distinguishing different gem materials on the basis of their recognized value. Diamond, emerald, ruby, and sapphire consistently have been regarded as precious stones, and in cut form they commonly are referred to as the noble gems. Opal, pearl, turquois, and chrysoberyl also have been classed as precious at various times. In recent years, however, it has been increasingly recognized that no satisfactory distinction can be based upon assessed value or any group of intrinsic properties, and at the present time all gem stones normally are referred to as precious. Indeed, the tendency is to extend this term to include many of the so-called ornamental stones, and the designation semiprecious has been essentially discontinued. Unlike most mineral commodities of economic value, gem materials are little altered in processing for end uses. Some stones are used in essentially their natural form, and most are reshaped and polished without significant changes in their fundamental properties. Thus the preparation of gem and ornamental stones is intended chiefly to emphasize or enhance desirable characteristics that are present initially. The worth of most synthetic gem stones is founded upon the identity between their major properties and the natural characteristics of the corresponding minerals, just as the pleasing qualities of imitation stones depend upon how well certain of their properties simulate those of more valuable substances. The most important specifications of gem materials represent four basic factors: beauty, durability, rarity, and portability. Beauty, whether expressed as splendor, "purity," attractiveness, or in some other way, is mainly a function of personal response to optical properties such as color, transparency, indices of refraction, and dispersion. Freedom from visible imperfections is important for transparent stones. For some substances beauty depends also upon asterism, opalescence, textural and

Jan 1, 1960

By R. F. Shurtz

The author proposes a method used with some success on a magnesite deposit at Gabbs, Nev. He believes this procedure to be more sound than the blind practice of assigning uniform quality to large, soinetimes vast blocks or ore on the basis of analyses made of a small number of samples. When an ore deposit is evaluated on the basis of core sampling, questions always arise as to how much weight should be given the various sample grades and how the deposit should be divided into specific volumes assigned to corresponding grades. For a tabular deposit it is customary to use the so-called zone-of-influence. This zone is usually defined as the polygon in the plane of the deposit having corners halfway between a given core drill intersection and each of the nearest neighboring intersections. The volume of the ore in this polygon is assigned the analysis obtained from the drill core taken at the intersection. In massive or irregular deposits, volumes of various shapes may be defined with respect to the locations of drill core samples. These volumes may be regarded as three-dimensional zones-of-influence; the theory involved in assigning the values of the central analyses to the ore in the volumes is the same as that used in the case of a tabular deposit. The zone-of-influence method was used in evaluating one of the magnesite deposits at Gabbs, Nev.'-"

Jan 1, 1960

By E. F. Adkins, R. I. Jaffee, C. T. Sims

The effect of oxide dispersions on mechanical proberties of cobalt and cobalt-base powder-metallurgy alloys was investigated. This study shows that oxide dispersions added to pure cobalt greatly improve the high-temperature creep resistance of the metal. Dispersions in powder-metallurgy .cobalt alloys were muck less effective. COBALT is extremely valuable as an alloy base for certain high-temperature applications. Important examples may be found in the widespread use of cast and workable alloys in aircraft gas-turbine engines. With the increases in cobalt production in recent years, greater use may be made of cobalt-base alloys for high-temperature applications, provided

Jan 1, 1960