Search Documents

By M. F. Williams, L. G. Hendrickson

IN classification of pulps bearing magnetized ferromagnetic particles, depolarizing is of great importance. If size separation is to be effective, particles must be individual rather than in floes. Depolarizing is also practiced in heavy medium separations in which ferrosilicon or magnetite is the medium. When particles of ferromagnetic material have been removed from a magnetic field, residual magnetism causes agglomeration. The term depolarizing refers to the operation of reducing or eliminating this residual magnetism and may thus be considered magnetic deflocculation. The terms demagnetizing and randomizing are also used. At the Research Laboratory of Oliver Iron Mining Div. in Duluth a method was developed for measuring depolarization of the pulp of ferromagnetic material. Experiments were made with Mesabi taconite,' a natural magnetite of low coercive force. Ferromagnetic materials of higher coercive force, such as lodestone or the artificial magnetite produced by reduction roasting of hematite, present a more difficult problem, which was not within the scope of this investigation. It is possible, however, that some of the techniques evolved for measuring and calculating electrical characteristics of alternating current coils would be of use in depolarizing high coercive force material, particularly in conjunction with high-frequency alternating current, as proposed by Hartig and others.'," Properties of Ferromagnetic Materials:'7 Experimental work, described below, has shown that if a sample in the magnetized state is heated above the Curie point and cooled, much of the preferred orientation is destroyed and the sample is substantially depolarized. It has been thought that when the sample cools below the Curie point the domains cancel each other, leaving a zero net moment. However, such particles still exhibit a tendency to cohere, and undoubtedly this is caused by the forces of residual magnetism. -AS measured by the percent depolarization, this tendency is reproducible for any sample upon repeated heating above the Curie point and subsequent cooling and is independent of the initial state of magnetization. It is postulated, therefore, that as the material is cooled below the Curie point the domains in any particle do not completely cancel each other, but rather are preferentially oriented to some extent. Mechanism of Depolarizing with Alternating Current Magnetic Fields: It is believed that when ferromagnetic material is passed through an alternating magnetic field, depolarizing occurs in the decaying portion of the field. As the particles pass through the portion of highest intensity they become magne- tized. If the particles are not free to move, the polarities of the particles will be reversed (by a mechanism similar to that described above for magnetism) at a frequency equal to that of the applied field. As the material moves through the decaying field, intensity levels become such that a domain does not completely reverse, but stops on an axis of easy magnetization. By the time the material reaches the point of zero field intensity, a state of fairly random orientation of domains is achieved. If conditions are such as to give a completely random orientation, the particle will have little or no external magnetic field, and a pulp of such particles will be depolarized. Previous Work In 1918 E. W. Davis was granted a patent for demagnetization of magnetite pulps.' His method consisted of passing the pulp through a tapered coil, activated by alternating current of normal frequency (60 cycle). This method, with minor modifications, has been used almost universally in all pilot plants and commercial installations in which depolarization of low coercive force materials has been required. Hartig, Onstad and Foot2,3 avd made a detailed study of the factors involved in depolarizing both low (below 100 oersteds) and high (above 100 oersteds) coercive force material. They developed a method for evaluating the relative degree of depolarization of any pulp based on the settling characteristics of the pulp. Their standard of comparison was a sample heated to above the Curie point and cooled in a zero field, all in a neutral atmosphere.* For low coercive force material they found treatment.Thisprocedure is subsequently called, in this report,theCurie that results equivalent to Curie treatment could be

Jan 1, 1957

Jan 1, 1957

By Lex B. Golden

The purpose of this investigation was to evaluate the corrosion properties of certain alloys of titanium and to compare them with those of unalloyed titanium. Such information should make it possible to determine the desirability of substituting these alloys for commercially pure titanium in certain applications. Titanium-manganese, titanium-chromium-iron, and titanium-vanadium-iron alloys, with 2 types of unalloyed titanium, I consolidated by arc melting and the other by powder-metallurgy techniques, were included in the study. Tests were carried out in sulfuric, hydrochloric, phosphoric, nitric, and mixed acids and in chloride solutions. All solutions were saturated with air.

Jan 1, 1957

Established as a Division November 17, 1948 B W Gonser, Chairman J C Kinnear, Jr, Past Chairman H H Kellogg, Chairman-Elect R C Cole, Vice-Chairman, '58 A E Lee, Jr, Vice-Chairman, '59 W R Opie, Vice-Chairman, '60 R W Shearman, Secretary AIME, 29 West 39th Street New York 18, N Y

Jan 1, 1957

By O. N. Carlson, H. A. Wilhelm, H. E. Lunt, J. M. Dickinson

On the basis of data obtained from microscopic examination, melting observations, cooling curves, X-ray analyses, and resistance measurements, phase diagrams have been proposed for the Th-Cb and Th-Ti alloy systems. Both are simple eutectic systems and have no terminal solid solubility or intermediate phases. The eutectic between thorium and columbium occurs at a composition of about 8 wt pct Cb and a temperature of 1435°C. The Th-Ti eutectic occurs at 1190°C at the composition 12 wt pct Ti. No change was observed in the transformation temperature of thorium in either system or in the titanium transformation. RECENT study of thorium and its alloys has been promoted because of the possibility of employing this metal in nuclear reactors. Their corrosion resistant properties, nuclear characteristics, and high melting points put columbium and titanium among the many metals being employed in the study of thorium alloys. Since a knowledge of the phase relationships would be important in the application of such an alloy, investigations were undertaken to propose phase diagrams for the Th-Cb and Th-Ti systems. Experimental Procedures Thorium metal sponge was specially prepared for use in this investigation. Carbon in a quantity less than 0.04 wt pct was the principal impurity. There was also less than 0.01 pct each of iron, calcium, zinc, aluminum, and nitrogen in the thorium. Columbium, both as a powder and sheet metal, was obtained from the Fansteel Metallurgical Corp. The manufacturer's specifications indicated that the metal contains less than 1 wt pct total impurities. An analysis of the metal showed approximately 0.18 pct C in the powder and less than 0.05 pct C in the sheet. The titanium used was commercial sponge, reported to be 99.5 pct Ti. An analysis showed that this metal contained 0.2 pct Fe. Preparation of Alloys—Since the metals used in this investigation are reactive and might become contaminated on melting in a refractory crucible, the alloys were prepared by arc melting. The titanium sponge was employed in the form of small lumps while the columbium additions were made either as pressed pellets of powder or as clippings from sheet. The alloying material and the thorium sponge were melted together under argon in conventional arc melting equipment employing a tungsten electrode and a water cooled copper crucible.

Jan 1, 1957

By Keats, J. L.

IN THE literature on the elimination of metalloids in basic open-hearth practice, there are a great many heats recorded in which excellent data on changes in slag and metal composition during refining are given, but in almost all of these heats either temperature data or weights and analysis of charge are unrecorded and observations on the physical charac- teristics of the slag are almost always lacking. With these points in mind, a test heat was made in which as complete as data possible on all the factors that affect the elimination of metalloids were obtained.

Jan 1, 1957

By Clyde L. Brown

Recent developments in portable communication equipment for use in emergency recovery work following mine fires and explosions have wade possible a convenient and dependable means of directing rescue teams working under hazardous conditions. INTRODUCTION Mine rescue and recovery operations following; fires and explosions are frequently conducted under adverse conditions that require the use of oxygen breathing apparatus by members of a 5- or 6-man team. Conventional apparatus used for this purpose for many years was equipped with an oxygen supply adequate for at least 2 hours. The design of the apparatus is such that the nose passages are closed with a clamp, and breathing is accomplished through a mouthpiece connected to the apparatus by tubes and arranged to prevent inhaling air or gases from outside sources. The use of the mouthpiece has presented difficulties in the development of telephone communication because of the wearer's inability to speak while wearing the mouthpiece. The method of conducting operations of rescue teams requires a person to direct operations at a fresh-air base as close to the rescue team as possible. At least one standby rescue team and 2 or 3 other persons assigned to various tasks are stationed at the fresh-air base. An efficient and reliable means of communication between the director of operations and the rescue team is necessary for reasonably safe and efficient work in hazardous areas.

Jan 1, 1957

By H. J. Modi, P. L. De Bruyn

IN recent years interest has been aroused in flotation rate studies both from a technical and a more practical aspect. With increasing fineness of grind becoming a necessity in treatment of low grade ores, difference:; in flotation rates of various size ranges will assume importance in the evaluation of overall recovery results. Theoretical analysis of flotation kinetics was initiated by Schuhmann,' who sought to define flotation rate of a given mineral and specified size range in terms of certain physical variables of the flotation system. Using as a basis for his analysis the bubble-particle encounter hypothesis previously advanced by Gaudin,' Schuhmann writes for the rate of flotation (R,.) of particles of average size x, Rx = PcPa(x) V F. [1] In this relation Pc and Pa represent, respectively, the probability of collision between particle and gas bubble in a given time interval and the probability of adhesion of particle to the bubble after collision. Rigorously speaking, the term PC does not have the significance of a probability factor, since it depends on the time interval and therefore can be numerically greater than unity. The term c(x) expresses the concentration of particles of an average size x in the flotation cell in weight per unit volume of pulp, and V denotes the total volume of pulp in the cell. The product, P,c(x)V, defines the frequency of particle-bubble collisl.on, and when it is multiplied by P,, the number of collisions per unit time resulting in successful adherence is obtained. The factor, F, measures the froth stability and is introduced because after fruitful bubble-particle contact some particles may still riot reach the froth launder. Coalescence of bubbles in the froth column or too short a bubble life could account for this effect. Schuhmann also introduced the concept of "specific flotation rate" (Q) to allow for the relative abundance of different mineral species in the flotation pulp. The specific flotation rate, having the dimension of reciprocal time, is defined as Eq. 2: Qx =Rx/c(x)v [2] and it also follows from Eq. 1 that Qx = PcPaF. [31 The theoretical aspects of flotation kinetics were also considered by Sutherland,3 who tried to improve Eq. 1 by expressing the probability factors in terms of such physical variables as particle radius (x), bubble radius (X), velocity of bubble relative to particle (v), the number of bubbles per unit volume of pulp (N) and the induction period (A) necessary for air-mineral adhesion. According to Sutherland's treatment, the rate equation, Eq. 1, transforms to R, = [3pX x v N] [sech2 (3 v ?/4 X) ] ?c(x) V [4] where the first term in brackets on the right-hand

Jan 1, 1957

Past President Robert L. Hair, General Superintendent, Coal Mines, Colorado Fuel & Iron Corporation, Pueblo, Colorado, opened the meeting at 10:00 a.m. "I will now call the Fifty-Third Regular Meeting of the Institute to order this morning and welcome the members and the guests. I'm on the program to introduce John Peperakis, President of the Institute for this year. I regret to announce that Mr. Peperakis received word this morning of an emergency at his mine and left to attend to this. We hope it is of a minor nature and he will return. (Editor's Note: Please refer to the index for printed text of the President's address which he had intended delivering, had he not been called away.) However, in the meantime, Robert von Storch has graciously consented to act as president until John Peperakis returns. "I needn't tell you who he is. Robert M. von Storch is General Superintendent of Coal Mines and Quarries, Columbia-Geneva Steel Division, United States Steel Corporation, Columbia, Utah. I now present Bob von Storch." Mr. von Storch: "As most of you know, the Rocky Mountain Coal Mining Institute cannot compare to the Mining Congress, as it is not a professional organization. It represents the coal operators in New Mexico, Utah, Colorado, Montana and Wyoming. We have a group of volunteers to put this together and use this occasion to get together and exchange ideas.

Jan 1, 1957

By D. E. Wolfson

As part of its overall program of coal carbonization, the Bureau of Mines is studying the coking properties of coals that may be used for metallurgical purposes. The objectives of this study were given in detail in a previous report.2/ The suitability of coal for metallurgical use depends primarily on (1) chemical composition, (2) preparation characteristics, and (3) carbonization behavior. The first two factors, as well as the available reserves, are considered in selecting coals for carbonization tests. According to the estimate of reserves by Dowd,3/ the recoverable coal in Raleigh County in beds 28 inches or more thick, in thousand tons, is: [ ]

Jan 1, 1957

By B. S. Butler

Apropos of metals low in the series illustrated by Dr. Butler's Table 11, it is interesting to note that Cress and Feldman29 reported traces of platinum metals in several samples of alunite. They found, chemically and spectrographically, several traces of platinum, palladium, and rhodium in alunite from Sugar Loaf Peak, near Quartzite, Ariz.; silver, platinum, and rhodium in alunite from Rio Grande County, Colorado; and traces of rubidium and gallium in various samples of alunite. These authors stated that the platinum metals appear to be present as Oxides and suggested deposition by hydrothermal solutions under near-surface conditions. AS described by Heineman,30 the wall rock of the Sugar Loaf alunite veins shows considerable alunitic alteration. Pyrite and hematite are relatively abundant in the wall rock but decrease progressively near the veins. Assays of samples of the Sugar Loaf alunite, run by J. B. Cunningham of the University of Arizona College of Mines, showed traces of silver and 0.002 to 0.004 oz of gold per ton, but the chemical form of the gold and silver in this occurrence remains undetermined.

Jan 1, 1957

By R. R. May

A preliminary examination of the Houston strip-coal mine, situated on the Alaska Railroad at milepost 175 (61 rail miles north of Anchorage, Alaska) and a review of all available information resulting from early coal exploration activities in the area resulted in plans to investigate the coal-bearing formations at depth by means of diamond core drilling to indicate the existence of additional reserves of coal in close proximity to railroad transportation, where it would be quickly available to meet rapidly expanding military and civilian fuel requirements. From the date of mobilization of equipment, August 28, 1951, until date of suspension, August 18, 1952, 2,010 feet of diamond drilling was completed. Ten definable coal beds were cut, of which 2 appear to be persistent and minable over an area of approximately 1/2 square mile. Within this area the 2 minable beds contain approximately 5,000,000 tons of coal in place. Of the remaining beds, at least two others may be minable to the eastward near their projected outcrops; however, these and deeper beds (at least in the vicinity of the drill holes) lie beneath a zone of pressurized gas and brackish water. From a practical standpoint, continued development and utilization of the coal in this vicinity will depend on the operators' ingenuity in developing cheap mining methods and on diligent prospecting for strippable coal under the comparatively light glacial cover.

Jan 1, 1957

Jan 1, 1957

By Bernard Rachlin

IN the mineral industry measurement of density or specific gravity of slurries is often necessary or highly desirable. To date the most successful method of measuring the specific gravity of various media is to hand weigh a constant volume sample of the slurry. This method is time-consuming, however, and is intermittent rather than continuous. Most density measuring instruments in use today are variations of three basic systems: air bubble tube systems, radioactive methods, and displacer systems. The high cost of the radioactive cell, combined with the precision electronic measuring that is required, limits the practical utility of this procedure to a small percentage of critical processes. In the air bubble systems clogging of the bubble tubes with solids has rendered this type of measurement completely ineffectual for many applications. Continuous or intermittent purging of the bubble tubes with air or water to prevent tube clogging has been tried but has not been very successful, especially in the heavy media process. The displacer system, which presents the fewest complications of all the density measuring systems, consists only of a metal immersion unit and a means of weighing it. In the past, settling of the solid in the slurry has caused untrue samples and clogging of the media at the bottom of the chamber. It is also important to dampen excessive flow surges such as those caused by reciprocating pumps. The system described here successfully overcomes these difficulties. Description of the Process System: The process equipment, on which the field tests were run, was a

Jan 1, 1957

By Nicholas J. Grant, H. C. Chang

EMPHASIS on the importance of grain boundary sliding as a mode of deformation at elevated temperatures has been presented elsewhere.' The extent to which boundary sliding occurs under certain creep conditions has been determined for high purity aluminum2,3 and aluminum alloys.' In general, boundary deformation extends quite far into the adjoining grains, resulting in a rather wide band of deformation along the grain boundaries. This has led some investigators to doubt that grain boundary sliding consists of shearing along the boundary surface; it has been contended instead that boundary sliding is a result of concentrated slip in the neighborhood of the deformed grain boundaries."' The purpose of this note is to present evidence that grain boundary sliding takes place by a bulk shear process. gh purity polycrystalline aluminum, wherever and whenever there is grain boundary sliding, boundary migration and concentrated deformation along both sides of the deformed boundary are associated with it. Therefore, it has been rather difficult to obtain unambiguous evidence of boundary sliding. On the other hand, it would be expected in certain alloys of aluminum, when tested under particular conditions. that the severity of the interfering effects of boundary migration and concentrated deformation along the deformed boundary might be reduced. Current research in this laboratory' shows that a 20 pct Zn-A1 solid solution alloy fractures in an intercrystalline manner during creep at 500°F with a small total elongation of not more than about 14 pct, and that it does so with extremely limited grain boundary migration. Accordingly, this alloy was chosen for the present study. The experimental procedure was similar to that used in previous work and has been presented elsewhere.' Two parallel flat surfaces were milled from a round specimen. The gage portion of the specimen was 1 in. x .09 in. x .17 in. The specimens, which were annealed at 1030°F for 24 hr, showed two to four grains across the width of the test bar. The specimens were subjected to creep at 500°F at stresses of 2000 to 5000 psi. The rupture times were from 10 sec to 3 hr. Appreciable boundary sliding occurred in all the tests. A typical example of boundary sliding is shown in Fig. 1. (The tension axis is vertical in the micrographs.) Sliding has taken place along the boundary between grains A and B unaccompanied by important boundary migration. The sharpness of the offset at the triple point can be clearly seen in grain C. As a result of sliding along the boundary between grains A and B, a new boundary surface between grains A and C was created. The offset at the triple point is about 0.07 mm. This boundary sliding is accompanied by the formation of rather sharp kinking bands and, of course, slip on several slip systems in grain C. This type of deformation has been referred to as fold formation' in previous work with high purity aluminum.

Jan 1, 1957

John P Hammond '59, President T C Frick '58, Past President Basil Kantzer '60. President-elect George R Gray '58, Vice-President Earl M Kipp '58, Vice-President G M Stearns, Treasurer Joe B Alford, Executive Secretary 800 Fidelity Union Bldg Dallas, Texas

Jan 1, 1957

By Frank C. Morris

It is generally recognized that the productivity and ultimate recovery of an oil well may be reduced as a result of reduction in permeability of the sand at the well bore by invasion of filtrates and clay particles from drilling fluids. As a means of determining whether a sand has been "damaged" from these sources, several investigators2 3 4 5/ have developed methods of analysis based on the rate of increase in bottom-hole pressure while a well is shut in. Because of growing recognition of the importance of completion practices as related to the quantity of oil that may be recovered from wells, the Bureau of Mines has studied completion practices in California and the Midcontinent area. Well-interference and pressure-buildup tests were completed Ear seven wells in the Scurry Reef field to determine the effective permeability in the reservoir.6/ Also, a study was made of the pressure-decline curves obtained from 35 water-input wells in 5 different production areas of northeastern Oklahoma and eastern Kansas.7/

Jan 1, 1957

By F. E. Jaumot, R. L. Smith

Self-diffusion in zinc at temperatures below 200°C has been studied using both single crystal and polycrystal samples. Anomalous results were obtained for single crystal samples, the data indicating that in some cases grain boundary diffusion predominated. These anomalous results are presumed to be due to low angle lineage boundaries in the single crystals. When volume diffusion occurred in either single or polycrystal samples, the values for the diffusion coefficient were as much as several orders of magnitude larger than would be expected from high temperature data. ONSIDERABLE work has been done on self-^-*diffusion at temperatures in the neighborhood of two thirds of the melting temperature (in OK) and higher, but very little has been done at lower temperatures. This is particularly true of self-diffusion in single crystals. This paper reports work on self-diffusion in zinc at temperatures below 200 °C where both polycrystalline and single crystal samples have been used. The measurements were made using both the sectioning and absorption techniques. The experiments on diffusion at low temperatures were initiated primarily for three reasons: to obtain data from single crystal diffusion covering a wide range of temperatures, to obtain values of the activation energy for grain boundary diffusion, and to obtain, if possible, a lower limit to the temperatures at which the absorption technique may be used. It is possible to determine whether volume or grain boundary diffusion predominates at low temperatures by analyzing the manner in which the concentration of the diffusing atoms varies with the depth of penetration. The analysis is possible only for the sectioning technique. For volume diffusion and for the boundary conditions of the present experiment, the curve of the logarithm of the concentration, C, vs the square of the penetration depth, x, is a straight line with the slope proportional to — 1/D. If grain boundary diffusion predominates, Fisher' has shown that a curve of In C vs the first power of the penetration depth should be a straight line. This linear dependence of concentration on depth has been observed experimentally by several investigators. (See, for example, refs. 3 and 4.) Following Fisher's analysis, the grain boundary diffusion coefficient can be written as where 8 is the grain boundary width, D, is the volume diffusion coefficient at the temperature involved, t is the time of diffusion, C is the concentration of diffusing material, and x is the depth of penetration. A more general analysis employing the same model as Fisher's but with fewer assumptions has been given by Whipple.' In contrast to Fisher's analysis the more general analysis of Whipple does not always yield a straight line relation between In C and x. Recently Turnbull and Hoffman have discussed both analyses and have applied the Fisher-Whipple model to a more refined dislocation model of the grain boundary. They have also discussed the possibility of a large effect of grain boundary direction on diffusion. In the case of the absorption technique, for which results are also given, one simply gets a value for the diffusion coefficient with no indication of the predominating mechanism. Experimental Techniques Single crystals of 99.99+ pct Zn were grown using a modified Bridgman method. Polycrystal samples were prepared in three grain sizes (small, about 4 mm2; medium, about 9 mm'; and large, about 25 mmz) by quenching, air cooling, and furnace cooling. The grains of the polycrystalline samples tended to be columnar, with some preferred texture such that the c-axis was inclined at about 20" to 25" from the normal to the diffusion face, particularly in the medium and large grain size samples. The samples were cut from the rod, polished, and heavily etched, and faces cut accurately parallel using a jeweler's lathe. They were again etched to remove the lathe smear and annealed for 3 hr at 250" to 300°C. After annealing, they were etched, examined, and the orientation determined by Laue back reflection photographs. They were then electroplated with Zn. The plated surfaces were examined for uniformity; nonuniform coatings were removed by etching and the samples replated without additional preparation. For the diffusion anneals, the samples were placed in pairs, with active faces together, in evacuated Pyrex tubes. Constant temperature baths were used, and the variation in temperature did not exceed ±l°C, Diffusion runs were made at l00°,

Jan 1, 1957

By Milton E. Wadsworth, Edward M. Eyring

BETTER understanding of solid surfaces and their associated adsorption products is of both academic and practical value. The study of detergents and their behavior in cleaning surfaces is fundamentally related to the nature of the products adsorbed and their ability to compete for certain surfaces. Similarly in flotation, the nature of the adsorbate before and after adsorption is basic to clear understanding of the process. The recently developed pellet technique1,2 employing infrared spectroscopy provides a powerful tool for the study of solid surfaces. Absorption bands, which are infrared-active, may be observed for adsorbed products. Also any changes in the surface substrate that occur as a result of adsorption may be detected by means of differential spectra. In applying the pellet technique to solids of large surface area, French and his coworkers3 have surveyed the adsorption of organic flocculants on clay minerals, oleic acid on fluorite, and ammonia on cracking catalysts. Recent work on application of differential infrared spectroscopy to the study of solid surfaces' has demonstrated that the difference between a sample and a reference can be obtained with double-beam instrumentation. In this way displacement of surface products, adsorption of new products, and differences in the substrate, if any, may be detected. Experimental Procedure: Potassium iodide pellets were used in this study, prepared from recrystallized analytical reagent grade KI. Grinding was carried out in a Fisher mechanical agate mortar. Two-gram plates containing the solid under study were pressed in a special evacuated die constructed in the laboratory at the University of Utah." Concentration depended on the solid in question. Zinc sulfide and willemite are sufficiently transpar- ent in the infrared region for concentrations as high as 20 mg of mineral in 2g of KI to be used. Zinc oxide is even more transparent, permitting concentrations as high as 60 mg in a 2-g plate. For non-differential operation, however, much lower concentrations (2 to 10mg/2g KI) had to be used. Spectra were obtained on a Per kin-Elmer 21 double-beam recording infrared spectrophotometer. A sodium chloride prism was used giving a spectral range of approximately 2 to 15 v wave length. For differential runs a resolution of 1000 was used and the scanning speed was controlled commensurate with instrument response. The response was checked continuously and each spectrum was repeated several times. For nondifferential runs a resolution of 927 was used. Zinc oxide used was analytical grade oxide fume. The zinc sulfide was precipitated from solution with analytical grade zinc sulfate and sodium sulfide. The precipitate was washed and centrifuged several times and dried. Before use the precipitate was washed in dilute HCl and then treated with saturated NH4Cl to remove any bulk oxides and sulfates. X-ray patterns of the precipitate were comparable to that of the natural mineral sphalerite. The precipitate was much more satisfactory than finely ground natural ZnS because of its very large surface

Jan 1, 1957

By D. L. Martin

THAT small amounts of impurities have a harm-J- ful effect on the malleability of metals and alloys is well-known. One common type of em-brittlement involves the formation of a small quantity of eutectic at the grain boundaries, and is typified by sulfur embrittlement of nickel. Another example of eutectic embrittlement—sulfur embrittlement of cobalt—is described in this report. In the preparation of specimens for a study of Co-Pt alloys, it was observed that the hot swagabil-ity of the alloys appeared to be influenced by the grade of cobalt used as melting stock. The cause of the hot-shortness was not traced to any particular impurity, although sulfur was suspected.' The damaging action of sulfur on the malleability of cobalt has not been generally recognized,'; in spite of the fact that the Co-S phase diagram8 eveals the same basic conditions—low solubility and eutectic formation—responsible for sulfur embrittlement of iron and nickel.7, 8 Apparently sulfur embrittlement has not been a serious problem in the fabrication of cobalt alloys. One related factor is likely the limited commercial experience with high cobalt alloys, since the predominant use of cobalt has been in alloys containing less than 75 pet Co. A series of Co-S alloys was prepared and studied to establish the effect of sulfur on the hot working characteristics of cobalt. Specimens, 5/8 in. diam by 4 in. long, were prepared by vacuum melting in magnesium oxide crucibles and casting in a copper mold. Two grades of low sulfur electrolytic cobalt were used as the basic material for the study, one from Johnson, Matthey and Co. and the other from the International Nickel Co. Each contained about 99.5 pet Co and had a nominal sulfur content under 0.005 pet. The sulfur was added initially as cobalt sulfide powder. Later, some low sulfur alloys were prepared by diluting the high sulfur alloys with cobalt. Trouble was experienced in controlling the sulfur content. Apparently much of the cobalt sulfide powder was lost during melting, as most of the samples contained a lower sulfur content than was added. The alloys were evaluated for hot brittleness by heating to 1000°C in a hydrogen furnace and swaging in air. The results of these tests are summarized in Table I. All the alloys containing less than 0.008 pet S were successfully hot swaged to 1/4 in. diam. The bars containing more than 0.015 pet S could not be swaged because of the formation of intercrystal-line cracks similar to those illustrated in Fig. 1. Examination of the microstructure of the cast bars revealed cobalt sulfide eutectic at the grain boundaries, Fig. 2. The sulfide was not always continuous at grain boundaries in bars that were hot embrittled but, in general, the particles did form a network that could account for the brittleness above the eutectic temperature, 880°C. There is no question about the brittle nature of a specimen exhibiting a continuous sulfide network such as is shown in Fig. 2b, though a sulfide distribution similar to that in Fig. 2a is marginal. This particular bar cracked when hot-swaged. However, other bars with lower sulfur content but with some sulfide phase at grain boundaries were successfully worked. The reduction of area of a hot tensile test specimen was also found to be a sensitive indicator of sulfur embrittlement. The variation of reduction of area with sulfur content is shown in Fig. 3 for specimens fractured at 900°C in an evacuated capsule. The ductility of cobalt is greatly reduced when the sulfur content exceeds 0.005 pet. Similar results were obtained for alloys tested at 800°C, below the eutectic temperature. The upper sulfur embrittlement limit of 0.015 pet, Table I, agrees with the observation of Kalmus8 hat

Jan 1, 1957