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By McQuiston. F. W., E. C. Tveter

Sulfide mineral flotation has been applied to all naturally occurring sulfides and several synthetics. Of even more importance is the fact that economic separations are now being made between sulfides of essentially all the different metals. The variety of methods and minerals involved in such practice make it difficult to characterize them except in terms of general factors which influence the practices used. Ore grade and mineral composition are the major factors determining the processing method and the extent to which processing must be carried to achieve optimum economic return for a given ore. Since the choice of treatment is also affected by such factors as mine location, shipping charges, smelter schedules, each ore is a separate problem even though mineralization may be similar; The dissemination of minerals in the ore naturally determines the fineness of grind required for liberation. However, since grinding costs are a major part of most milling costs, emphasis has been placed on means of rejecting gangue minerals at the coarsest size possible. This has led to increased flotation of middling products or bulk concentrates for subsequent regrind and retreatment. Reagent development has also played an important part in present plant practice. Relatively few new frothers and collectors have found application during the past 25 years and many have disappeared. In general practice, re- agent combination choice is now fairly consistent with the type of collector being chosen on the basis of the mineral to be floated, the frother on the basis of pulp alkalinity, and the modifiers primarily on the basis of minerals to be rejected. REPRESENTATIVE FLOTATION PLANTS The milling operations described in this chapter have been selected primarily to illustrate these differences in ores and processing methods for the major types of ore minerals. The compositions of these minerals are shown in Table 1. These concentrators were chosen as representatives, both on the basis of geographic location and mineral content of the ore treated. At least one mill is included from each of the major producers, but the primary object was to show the practice employed for the various ore minerals and the different approaches to the middling problems encountered. The individual plants which have contributed data to this study are listed in Table 2, with a summary of their operating data, and are discussed in the order shown.

Jan 1, 1962

By J. Gordon Parr, A. J. Goldak

OgdEN et al.1 and Bumps et al.2 suggested that the solubility of aluminum in a titanium extended to 30 pct.* Sagcl,3 Clark and Terry,4 Anderko et al.,5 Ence and Margolin6 and Saulnier and croutzelles,7 subsequently proposed the existence of an intermetallic compound in the region of 25 pct Al. Although Anderko et al.5 suggested that the structure of this phase, Ti3Al, was of the DO,, (Ni3Sn) type, their conclusion was based only upon the results of a powder photograph that included reflections from ? = 0 to ?= 27° (CuK),some of which were reported to be indistinct. Ence and Margolin,6 referring to a 25 pct alloy (but without indicating whether the figure referred to weight or atomic pct) stated: "The structure of Ti2Al is isomorphous with Ti3Sn DO19, as pointed out by Pietrokowsky". But the point was not proven, because Ence and Margolin did not report values of calculated intensities of Ti2Al with the DO,, structure. In fact, the observed intensities they reported are in poor agreement with the values we calculate for DO19 (see Table I). Saulnier and croutzelle7 concluded, on the basis of electron micrography and microdiffraction studies, that the structure of the 25 pct A1 alloy was ordered hexagonal. Our purpose has been to unequivocally determine the Ti3Al structure. Alloys containing 25 pct Al were prepared from iodide titanium and spectrographic standard aluminum by levitation melting. The levitation chamber was evacuated to 10-6 mm Hg before filling with 99.999 + pct A. After casting, the alloy was chilled to liquid air temperature and crushed to -200 mesh in a percussion mortar. The powder, wrapped in molybdenum foil, was annealed (by induction heating) at 1000 "C for 2 hr in the argon atmosphere of the levitation chamber. No sublimate was seen on the foil or elsewhere, and therefore the assumption is

Jan 1, 1962

By A. B. Whitehead

A spectrographic method for the determination of 18 impurities in cerium is presented. The carrier distillation technique is utilized to separate the spectra of impurities from the complex spectrum of cerium. Metal samples are ignited to the oxide, mixed with silver chloride carrier containing an internal standard, and excited with a 20-ampere direct-current arc. An additional exposure, made after carrier depletion, provides for the determination of refractory elements. Experiments to determine the best carrier, sample-carrier ratio, electrodes, arc current, exposure conditions, internal standards, and any matrix effect are described. The relative standard deviation of the method at the 20- and 200-part-per-million levels is about 25 and 15 percent, respectively. The average relative error is about 20 percent in the 10- to 1,000-part-per-million concentration range.

Jan 1, 1962

By Paul M. Clifford, David M. Baird

The Great Northern Peninsula of Newfoundland consists of a Precambrian core of gneisses and granitic rocks, cut by numerous diabase dykes. This complex is surrounded by an envelope of sedimentary rocks of Cambrian to Carboniferous age. Radiometric dates from two granite masses in the core give a mini-mum age of -945 m.y. (Grenville) for the last major tectonic activity. This Grenville deformation conferred upon the core substantially its present structure which has controlled later events to a marked degree. Block movements of the core, dominantly in a vertical sense, have ex-posed it to erosion at intervals. The nature and distribution of the flanking sedimentary rocks and the present relief of the peninsula suggest four such movements. THE Great Northern Peninsula extends some 150 miles north-northeast from the northwest corner of the main body of the island of Newfoundland. It separates the Gulf of St. Lawrence from the Atlantic Ocean, except for the 12 mile wide

Jan 1, 1962

By William F. Tanner

A river delivers a given load of sand, and hence of heavy minerals, into the sea into which it empties. This load is fixed by drainage basin characteristics and processes. Wave energy available for redistributing that load is fixed in an entirely different way. An equilibrium diagram of these two parameters (load versus energy) permits a tentative prediction of what will happen to the heavy minerals. The Chattahoochee River delivers a load which, over the past few thousand years, appears to have been greater than the available coastal energy could handle. As a result, much of the sand has been accumulated in various delta-margin features: barrier islands, beach ridges, and large furrowed off-shore shoals. The bulk of the trapped sand is found today in the shoals, which are attractive deposits for possible exploitation. If coastal energy levels are high enough to move the total load delivered by the river, accumulations of sand (and hence of heavy minerals) should be sought in the down-drift direction. Energy levels are rarely constant over any great length of coast. Decreases in energy may be due to widening of the shelf, convexity of, the shore, restrictions on the fetch, wave decay, or other causes. Such decreases result In deposition. Hydrodynamic mapping of coastal areas, as outlined here, should prove useful in the location of additional reserves. Part of this type of work can be done on maps, charts, and air photos.

Jan 1, 1962

By J. H. Smith, H. W. Paxton

X HE recent investigation of Butler, McCabe, and paxton' on the vapor pressure of manganese gas in equilibrium with Mn-Fe alloys has been extended to include the iron-rich solutions and alloys in the two phase equilibrium region. The study of the phase equilibrium by Kurnakov and Troneva2 and the extensive reviews of the Mn-Fe system by Hansen,3 and Hellawe114 are not in agreement with regard to the location and extent of the equilibrium between the solid phases of fcc y and complex P in the temperature range above the eutectoid temperature of approximately 975Kwhere 0 decomposes to y and bcc a. An evaluation of the existing equilibrium data is confronted with the conflicting results presented by various investigators who used techniques requiring a quenching treatment to retain the high-temperature equilibrium or encountered temperature hysteresis during thermal analyses. The difficulty of suppressing the transformation of the manganese-rich concentrations of the y-solid solution during quenching has been well etablished.' To avoid this uncertainty the phase equilibrium was investigated at temperature by measuring the partial pressure of manganese gas in equilibrium

Jan 1, 1962

By Gerd L. Klinkenborg

Throughout the history of the development of mechanical conveyor systems, it has always been an established condition that loads are received at one end of a single-belt conveyor and discharged at the other end, in a point-to-point, manner. In systems designed for the continuous transport of granular materials, vertical or horizontal changes in; direction have always necessitated two or mope single-belt conveyor units, with a corresponding number of motors, assemblies and attendant mechanical and human or electronic controls. Besides these high-cost factors, every change in the system's direction also calls for a transfer point that involves a drop-back of the material from one level to another with some loss of the material and, in many cases, unwanted additional granulation. Where changes in the location of the discharge point are wanted, the conventional single-belt conveyor must either be replaced by a shorter or longer unit or additional units purchased and installed, or existing units rearranged. This can take days or weeks, and involve special expenditures as well as loss of valuable production time.

Jan 1, 1962

By R. Q. Shotts

This paper is a review of recoverable reserves of bituminous coal in the Southern Appalachian area, according to the latest published estimates. A few comparisons are made, some apparent trends are discussed, and some comments are made regarding the limitations of present estimates. The definition of Southern Appalachian area used in this report is somewhat arbitrary. It includes all the bituminous coal deposits of Alabama, Georgia, and Tennessee. All of West Virginia has been excluded. The East Kentucky and Virginia counties included were selected in connection with a literature study the writer made in 1959 of possible coal supply areas for the Tennessee Valley Authority. The selected counties were considered to be the only ones from which TVA might expect to obtain coal. The availability of coal from some of these counties is doubtful, but no other East Kentucky counties were considered more than remote possibilities. With these limitations, the Appalachian area covered is that from which producers of electric power and steel and commercial coal users, located in the Southeastern U. S., may expect to obtain their supplies of coal. Of course, it is recognized that coal from the eastern interior fields is also available to many of these same organizations. RANK AND QUALITY OF THE COALS Practically all the coals in the Southern Appalachian region are of high volatile A bituminous rank. An occasional sample indicates a slightly lower rank, but such samples may be oxidized or otherwise not representative. Some thin beds in Lookout Mountain and Sand Mountain in Alabama and Georgia, are low volatile bituminous coals, but they have not been mined extensively in modern times. There is a possibility that some of the deeper beds along the southeastern edge of the Warrior field of Alabama are near the Low-medium volatile bituminous dividing line. The Sewanee bed and some other minor ones of the Southern Tennessee field, some of the lower beds in Virginia, many beds in Sand and Lookout Mountains in Georgia and Alabama, one or more beds in the Coosa field, possibly some lower beds in the Cahaba field, and most of the beds along the southeastern edge of the Warrior field and the southern end of the Sequatchie anticline of Alabama, are of medium volatile bituminous rank. The quality of the Southern Appalachian coals is highly variable. Some of them, particularly such prevailingly thin ones as the Black Creek bed of Alabama and the Straight Creek bed of Kentucky, are unusually low in mineral matter— probably the lowest in the U. S. With the exception of certain beds and local areas, Alabama and East Kentucky coals probably have as low average ash and sulfur content as can be found in any sizeable coal area in the country. The sulfur content of Southern Appalachian coals is also variable, but few beds are consistently high in sulfur. In Alabama, sulfur generally increases from southeast to northwest across the Warrior field, but this trend is not quite as clear in the other states. A few beds in Northern Tennessee are prevailingly high in sulfur. All Southern Appalachian coals are potential coking coals if they can be prepared to meet chemical requirements. Only a comparatively small part of the medium volatile A bituminous coal, but most of the medium volatile bituminous coal mined is actually used for coking purposes. An estimate of reserves of coking coal under the requirements of present practice, could be compiled comparatively easily, but this probably has never been done. The reserve of coal that can be coked as an ingredient of a suitable blend is probably many times the size of the reserves of coal that will yield suitable blast furnace and foundary coke without blending. WHAT CONSTITUTES ECONOMICALLY RECOVERABLE COAL RESERVES? When one first realizes the vast extent of the coal-bearing rocks in the Southern Appalachian area, (see Fig. 1) the thought is likely to occur that the supply of coal is inexhaustible. This is particularly true on realizing that in some of the basins of thicker coal-

Jan 1, 1962

By Joan T. May

Anhydrous methods were tested for the extraction of beryllium from low-grade source materials. The purpose of the investigations was to find new extraction processes that are applicable to domestic ores. Beryl, helvite, and phenacite materials containing from 0.1 to 2.8 percent BeO were used as starting materials for direct halogenation tests and pretreatment followed by halogenation. The results of the investigations showed that direct fluorination and carbide-chlorination are two practicable methods that can be applied to low-grade concentrates. Treatment of concentrate-carbon mixtures with anhydrous hydrogen fluoride extracted 99 percent of the beryllium in the concentrate; the soluble fluoride product, converted to an oxide, contained 70 percent BeO. Chlorination of beryllium-silicon carbide, prepared from low-grade concentrates, extracted beryllium into the volatile chloride product.

Jan 1, 1962

By M. M. Fine

This report describes a Bureau of Mines technical feasibility study of simultaneous reduction and induration of pelletized iron ore to make a product with superior qualities as blast-furnace feed. Highly reduced, physically competent pellets can be made from magnetite and specularite concentrates that contain small additions of bentonite as binder. In batch tests, pellets were dried, surrounded with solid fuel in crucibles, and heated to the reducing temperature. Total iron content of the best products was higher than 80 percent and crushing strength of 1/2-inch metallized pellets ranged up to 600 pounds or more. Comparative tests of several commercial oxide pellets showed a wide range in crushing strengths, but most values were less than 350 pounds. Continuous tests in a rotary kiln resulted in the same degree of reduction, but the pellets had lower crushing strengths because of the limitations in the maximum operating temperature of the small kiln.

Jan 1, 1962

By A. Zrimsek, G. Vingas, R. Wolke

IN 1952, prompted by the great demand of the Canadian drilling and foundry industries for sodium bentonite, the Geological Department of Magnet Cove Barium Corporation, Limited began an extensive search for bentonite deposits throughout western Canada. Their efforts were rewarded in 1958, when substantial deposits of high quality material were found approximately 100 miles southeast of Edmonton, Alberta. The bentonite material, a part of the Edmonton formation in the Upper Cretaceous, is located approximately nine miles south of the town of Rosalind. The land where the bentonite lies has in places .been eroded by stream and glacial action to form a wide gully, convenient for strip mining methods (see Figure 1). The bentonite bed is almost flat-lying, dipping to the southwest at approximately 12 feet per mile. The main bed is 8 to. 10 feet thick and is covered with 15 to 25 feet of overburden. Before stripping, the area is drilled and sampled to evaluate the quantity and quality of the bentonite.

Jan 1, 1962

By J. A. Harrison

Most coal being used in the United States has been subjected to one or' more processes of coal preparation. The physical and chemical characteristics of a coal have a marked influence on the ultimate uses that coal may have. The selection of the proper preparation processes may similarly be important in producing the best practical coal product for any particular use. The physical composition and distribution of physical constituents in the coal will partially determine the efficiency of the preparation process chosen and conversely distribution and concentration of coal macerals will, to a degree, be controlled by the preparation process. A number of preparation processes have been evaluated to determine this interrelation. If a coal having' certain specifications is desired, these evaluations trill assist in providing information needed for the production of this coal.

Jan 1, 1962

By David E. Fogelson

One model each of three different makes of portable displacement seismographs was calibrated on a shaking table capable of 5,000 pounds of force, Calibration tests were conducted in the frequency range of 5 to 200 c.p,s, and in the amplitude range of 0,002 to 0.05 inch peak-to-peak, The seismographs were tested under two mounting conditions: (1) The feet of the instrument were bolted to the shaking table, and (2) the feet were resting on emery cloth affixed to the table, The results of these tests show that, in the frequency range of 5 to 40 c.p,s, and for vibration levels less than 0.2 g, the magnification for all three instruments is constant with input level but varies slightly with frequency. For vibration levels greater than 0.4 g. and for frequencies greater than 40 c.p.s., the magnification of all three instruments shows large variations with frequency and amplitude of table motion.

Jan 1, 1962

By A. A. Berk

The Bureau of Mines devised a test nipple for the field study of corrosion in the condensate-return lines of Federal heating plants. Corrosion surveys, made with this device, showed that the deterioration of the piping was caused principally by carbonic acid in the steam condensate. Corrosion problems were brought under control when the carbonic acid concentration in the condensate was decreased. In many instances, this was effected by decreasing the total carbon dioxide content of the feedwater; in others, the condensate acidity was neutralized with volatile, alkaline chemicals. Filming treatment with octadecylamine, reported successful in controlling return-line corrosion in industry, was much less effective in Federal area-heating plants. Laboratory study by the Bureau disclosed that octadecylamine is unstable in heating systems. Analytical methods were developed for this chemical and its degradation products in heating-plant condensate. Field surveys, in using these methods, confirmed the instability of the filming material. Laboratory tests showed that the degradation products are not useful film formers. Since filming treatment has little effect on condensate corrosivity, the piping was corroded where it was not coated by the treatment chemical.

Jan 1, 1962

By Sarkis G. Ampian

The Bureau of Mines has developed a method for identifying fine particles of beryl in mineral samples by preferentially staining the beryl grains. The sample is first subjected to a heated sodium hydroxide solution to etch the beryl particles, which are subsequently stained an intense blue color in a boiling alkaline solution of quinalizarin. Positive identification of beryl grains permits quantitative analyses by microscopic techniques. INTRODUCTION Beryl, a beryllium aluminum Silicate, is the principal ore mineral of beryllium. The only known commercial concentrations of this mineral are found in pegmatite dikes of granitic composition. Normally beryl is associated with muscovite mica, quartz, and the sodium-and potassium-bearing feldspars (orthoclase, microcline, and albite). Other beryllium-bearing minerals which are found occasionally in minor amounts with beryl are phenacite, a beryllium silicate, and chrysoberyl, a beryllium aluminate.

Jan 1, 1962

By D. N. Seidman

In the course of a study of the electronic and thermodynamic properties of Pb-Se alloys it was found necessary to have an accurate knowledge of the phase diagram. However, the literature is in disagreement as to whether or not a monotectic reaction occurs in the lead rich portion of the phase diagram. Pelabonl reported only a two-phase region consisting of lead-rich liquid and solid PbSe extending from almost pure lead to the compound PbSe, and gave the melting point of PbSe as 1065°C. The data of Friedrich and Leroux2 are in general agreement with this type of diagram, with the melting point of the compound being 1088°C. However, Nozato and Igaki by inverse rate thermal analysis observed a monotectic reaction isotherm exlacing at 860°C with a monotectic composition of 20.5 at. pct Se. The miscibility gap in the liquid state extends from 7.5 to 20.5 at. pct Se. Hansen and Anderko4 accepted Nozato and Igaki's phase diagram in the region of the lead-rich monotectic. To reinvestigate this portion of the phase diagram, both thermal analysis and metallographic examination of various compositions were performed. The thermal analysis apparatus was constructed according to the specifications of the National Bureau of Standards. A t/t-l pct Rh thermocouple was calibrated against the melting point of copper (NBS), zinc (NBS), and antimony (A. D. Mackay), the emf being measured with a Rubicon Type B potentiometer sensitive to lpv. The absolute accuracy of the thermal analysis obtainable with this system is ± 0.5oC. Starting materials were semiconductor grade lead and selenium purchased from the American Smelting and Refining Co. Both elements were 99.999 pct pure with only trace impurities detected upon spectroscopic examination. One hundred galloys were sealed in quartz crucibles with a central thermocouple well under a vacuum of less than 1 p. This procedure prevented any composition change due to vaporization during the run. Cooling curves were obtained on the alloys listed in Table I. Data was taken by the direct method at cooling rates ranging between 1/2 to 2°C per min. The alloys were heated well above the liquidus and shaken vigorously to insure homogeneity. No evidence of an arrest indicative of the monotectic reaction was observed, and the two-phase region reported by Pelabonl and Friedrich and Leroux? was confirmed in general, although our data give higher liquidus temperatures than Friedrich and Leroux. The melting point of stoichiomet-ric PbSe determined for two different samples was 1080.7 0.5oC. The results of this investigation are compared with Nozato and Igaki's data in Fig. 1. To Complement the thermal analysis data, an 86 at. pct Pb specimen was examined microscopically. This composition was in the center of the miscibility gap reported by Nozato and Igaki.3 The alloy was heated to 1000°C, held for 1/2 hr, and water quenched. The specimen was polished using standard metallographic techniques for lead. The alloy was etched with an acetic-nitric acid etchant for 10 min at 45°C. Microscopic examination did not indicate the existence of two separate layers or solidified droplets imbedded in a matrix, as would be expected if a miscibility gap were present. The mi-crostructure shown in Fig. 2 consists of uniformly dispersed, dendritic PbSe in a lead-rich matrix.

Jan 1, 1962

By Whitehead A. B

INTRODUCTIONDuring the past few years there has been considerable interest in developing the so-called direct reduction processes for treating iron oxides. The various methods proposed were recently reviewed by Scortecci and Palazzi (1960).In particular the application of fluidized bed techniques received considerable attention and, on first examination, this seems to be the ideal method 'of dealing with fine iron oxides. Several difficulties (e.g. product agglomeration) require the method to be investigated further before its potentialities can be fully assessed.PROPOSED FLUIDIZED BED REDUCTION PROCESSESBrassert and De Jahn (1951) were among the earliest to suggest the use of fluidized beds for the reduction of iron ore to metallic iron. Their patent was followed by many others proposing similar concepts, mainly from Lewis (1955), Ogorzaly (19.56), Shipley (1956), Agarwal (1960'), Osborn (1958), Texaco Development Corporation (1956) and Stelling (1957).The H-iron process (Squires and J ohnson, 1957; Lubker and Bruland, 1960) is the only scheme that has been an economic success. This process, mentioned later, manufactures a 'premium quality product in the form of sized iron powder.AIM OF THE PRESENT WORKThe work reported here was performed to assist in the formulation of a comprehensive pl'ogramme of research into fluidized bed reduction processes to be undertaken at the...

Jan 1, 1962

By W. L. Freyberger, R. B. Booth

Froth flotation is a chemically induced method for beneficiating or up- grading an ore, which utilizes a layer or column of froth as a separating medium to segregate and remove the valuable minerals from the worthless gangue components of a finely ground ore suspended in water. The object of this chapter is to discuss the theoretical aspects of froth formation, the various frothing agents employed in flotation, and the effect of chemical structure on froth formation, and to correlate these factors with flotation technology. The flotation method of separation is conducted in three main steps: 1) selective chemical modification of the surface of specific mineral particles to effect floatability or nonfloatability; 2) contact between air bubbles and mineral particles, the selective adherence of floatable minerals to these bubbles, and the rejection of nonfloatable minerals; and 3) separation of the floatable minerals from the nonfloatable minerals. As indicated above, these three operations are achieved by the use of chemicals. Frothers play their most important role in the second and third steps by influencing particle- bubble contact and by affecting the degree of separation obtained in the froth column. Frothers, as defined by flotation operators, are compounds that are used specifically for the purpose of creating a froth in a flotation separation. How- ever, some collectors produce froths that are adequate for some flotation operations. Although this chapter is chiefly concerned with the specific frothers used in flotation, some discussion of frothing collectors is included. Otherwise, collectors (or promoters) and modifiersare not discussed at length; for information on these types of flotation chemicals, the reader is referred to other sections of this book or to other sources.l HISTORICAL DEVELOPMENT OF FROTHING AGENTS Historically, there are two distinct phases in the development of frothing agents and other flotation chemicals: 1) 1860 to 1920-oil flotation, and 1921 to date-chemical flotati0n.2~3 Early in the first period, large quantities of fatty and oily materials, up to 10 to 20% of the weight of the ore, were used as a means of separating the sulfide and oxide components from the gangue minerals in ore pulps. Later, various gases replaced these large quantities of oil as a buoyant and separating medium, decreasing oil requirements to less than 1% of the weight of the ore. With this reduction in oil

Jan 1, 1962

By J. S. Kirkaldy, D. G. Fedak

The extra degree of freedonz introduced by a second independetzt concentration in a tenzary system gives rise to the possibility of unstable planar phase interfaces in semi-infinite diffision layer couples. Diffusion paths which pass continuously in and out of too-phase regions of the phase diagram but which are not coincident with tie-lines give rise to super saturated zones which may be either adjacent to or isolated from planar phase interfaces, with corresponding nonisolated or isolated precipitates. Nonisolated precipitates are equivalent to morphological development of the interface. Selected couples in the ternary systems Fe-Ni-Cr and Cu-Zn-Sn have been examined nzetallographically and ifz the latter case both isolated and uo~zisolated precipitates have been observed. The diffusion path in one of the couples showing interface morphological developtnent has been examitled using electron probe microanalysis. IGNORING the spurious effects of preferential grain boundary diffusion and anisotropic crystal growth7 it can be unequivocally stated that it is impossible for a binary isothermal diffusion couple constructed of two unsaturated phases to sustain a nonplanar phase interface. Consider for demonstrative purposes the schematic phase diagram of Fig. l(a). Given an initial flat phase interface, semi-infinite boundary conditions and the internal boundary condition fixed by the constitution diagram, xB = xB(T), the unique solution of the diffusion equation requires a persistent flat interface. No other solution is possible. If, however, we anticipate the involvement of surface tension, then the internal boundary condition must be written xB = xB (T,Y) where r is the radius of curvature of a hypothetical nonplanar interface. The introduction of a new parameter such as r can be equivalent to the release of an internal constraint, so that a stable nonplanar interface may be possible after all. Consider a perturbation to the interface as indicated in Fig. 1(b). According to the Ostwald-Freundlich equation: which is applicable to a system of this constitution, the solubility of A in the matrix ß ,xB (Y), at a point of curvature r is given by where Va is the molar volume of the a-phase, R is the gas constant, and a is the interfacial tension. Since the right hand side is positive, xB(r) >xB cm, as indicated in Figs. 1(a) and 1(c). Accordingly, the perturbation will carry the interface concentration in a direction which is opposite to that which would sustain local equilibrium. Such a perturbation is necessarily moderated and the system is returned to its initial condition. This result is general for all binary couples since we can regard an interfacial perturbation as an attempt to precipitate within un-

Jan 1, 1962

By R. J. Sherman, M. R. Achter

Creep rates have been measured for nickel at 1200°F in air and in vacuum, and related to the depth of surface cracks in the specimens tested in the two environments. The surface cracks were observed to grow faster in air than in vacuum in both short-time and long-time tests. Crack depths, however, could be correlated with creep rates only in the short-time tests. Although no cracks were observed in a relatively brittle Ni-Cr-A1 alloy creep tested at 1300°F, the appearance of alloy specimens fractured after interruption in creep indicated that there was a decrease of intergranular cohesion resulting from the diffusion of atmospheric gases into grain boundaries. PREVIOUS investigations1-3 have demonstrated that the effect of atmosphere on the high-temperature strength of nickel and nickel-base alloys may be reversed by changes in the stress or temperature of the test. At high stress and low temperature the creep-rupture life is longer in vacuum than in air, while at high temperature and low stress the relative strengths are reversed. A mechanism to explain this behavior was proposed based on two competing processes. Oxidation hardens and strengthens a metal, but adsorption of gas, by lowering surface energy, reduces the work required to propagate an intergranular crack. The controlling process is determined by temperature and stress. Basic to this mechanism is the concept that environment determines the ease of propagation of intergranular cracks and thus affects creep rate and rupture life. To explore the mechanism in greater detail, this investigation was undertaken to determine the effect of atmosphere on crack initiation and propagation rates in nickel1 and a relatively brittle Ni-Cr-A1 alloy.3 EXPERIMENTAL PROCEDURE The materials were the same as used previously. Nickel of 99.8 pct purity had the following impurity content: 0.02 pct Co, 0.03 pct Fe, 0.02 pct Mg, 0.03 pct Si, and 0.008 pct C. Rods were cold swaged from 1/2 in. to 3/8 in. in diam and machined into speci- mens with gage sections 1/4 in. in diam by 1-1/4 in. long. They were annealed in vacuum at 1600" F for 1 hr to achieve a grain size of 0.07 mm. The alloy was composed of 19.1 pct Cr, 3.6 pct Al, 1.7 pct Si, 0.57 pct Fe, 0.10 pct Mg, 0.027 pct C, 0.004 pct S, and the balance Ni. Sheet specimens of 0.500-in. width and 1.25-in. gage length were machined from 0.033-in.-thick strip and annealed in vacuum at 2000° F for 2 hr, resulting in a grain size of 0.036 mm. Large amounts of an intergranular phase were introduced as a result of the anneal. Creep tests on both materials, using equipment previously described by Shahinian; were conducted in air and in a vacuum of 1 x 10-5 mm Hg. They were continued to rupture and interrupted at various stages of the test. Although extensions were measured from dial gage readings of movement of the lever arm, it is considered that valid comparisons of creep rate may be made in this manner.l Two parameters were measured metallograph-ically* on longitudinal sections of nickel specimens interrupted during creep—the mean depth of surface cracks 2, and the density n as the number of cracks per unit length of surface. They were combined into one parameter by the relation p = n-d [1] As used here, p is equal to the total of crack depths per unit length of surface. RESULTS Nickel. It is well known that the incidence of intergranular cracking is increased with increasing rupture life. Indeed, it is evident in Tables I and I1

Jan 1, 1962