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By Alexander Knoll, Dwight L. Baker

THIS paper is a report on work undertaken to investigate the results and conclusions of Ravitz and Porter1,2. that galena freed of surface oxidation products and lead carbonate ("clean" galena) is water-repellent, and that the action of xanthates in flotation is the action of a cleansing agent, enabling oxidized galena particles to expose a pure lead sulphide, water-repellent surface. The apparatus, in construction and use, was essentially that of Ravitz and Porter. The only significant modification introduced by the present authors was the substitution of a three-necked flask for the flotation cell as the "reaction vessel." Our procedure was to place 50 grams of freshly ground, minus 200-mesh galena in the reaction vessel, sweep out all molecular oxygen from the system with oxygen-free nitrogen, and proceed to wash the galena surface free of its oxidation products with repeated small portions of (I) ammonium acetate (500 c.c. of water, 200 grams of ammonium acetate) or (2) ammonium chloride, hydrochloric acid (2 liters containing 200 grams of ammonium chloride and 25 c.c. of 1.18 sp. gr. hydro chloric acid). The galena was next washed with many 100-c.c. portions of oxygen-free, distilled water. The galena was finally considered free of soluble salts when wash water that had been in contact with the mineral for at least 48 hr.* gave negative tests for: (I) lead ion with sulphide; (2) chloride with silver ion; (3) acetate with cuprous chloride, sodium chloride; and (4) ammonium ion with Nessler's reagent. Next 500 c.c. of potassium ethyl xanthate solution, free of dissolved oxygen, was run onto the "clean" galena particles. For this system there were determined: I. The wetting properties of the clean galena particles by shaking the reaction flask and noting the degree of mineral collection at the liquid-air interface. This was, of course, simply a qualitative test, but it proved adequate for our purpose. 2. The removal of xanthate ion from the potassium xanthate solution on being shaken with the "cleansed" mineral. Xanthate concentrations were determined by iodine titration according to the methods of Taylor and Knoll.3 3. The pH of the xanthate solution after having been shaken with the "cleansed" galena. The pH was determined colorimetrically.4 The results of five experiments of the type mentioned above are given in Table I.

Jan 1, 1941

By Robert H. Richards

(Read at the Wilkes-Barre Meeting, May. 1877.) THE Institute of Mining Engineers has shown so much interest in the educational problem of profitably combining theory and practice, that it seems especially appropriate to lay before its members the methods and aims of the mining laboratory of which I have charge, and in which one form of combination of hand with head work is now being tried. If anything may be contributed toward the solution of this problem by the discussion which follows, my purpose will be attained. Whether it was wise or not to establish a mining school so far from the principal mining centres, does not now enter into the question. Given, a mining school already begun, how shall it be made most efficient in developing engineers who are trained to think for themselves as well as versed in the works of others? This is the ques¬tion with which we have had to deal. In considering the bearing of this laboratory work upon the students' preparation, it will be convenient to take it up under five different heads 1. The methods and aims of the laboratory. 2. The advantage to students of having a part, at least, of their practical work in the curriculum of their school. 3. The advantage to be derived by mines and works. 4. Degree of accuracy which may be attained in working ores on a small scale. 5. Results of work in the laboratory. 1. The Methods and Aims of the Laboratory.-During the May meeting of 1873, held in Boston, I had the privilege of reading before you a paper stating the plans and aims of this laboratory. Since that time we have been constantly following out those plans, and are more than ever convinced that we are working in the right direction. We do not feel that the time we have spent has been in any sense thrown away. Perhaps the aims of the laboratory can be most clearly shown by illustration. Many young engineers leave school thinking that they know everything. They go to the works, and expect to teach the superintendent something and the men a good deal, regardless of the fact that it is this spirit that has prejudiced workmen against schoolmen. They are often more trouble than they

Jan 1, 1878

By F. L. Sizer

The mining regulations of British Columbia and Mexico present some features which might well be copied in the United States, if we are to have a complete revision of the laws governing mining titles. 1. First and foremost is the "squarc" location, which would mean the abolition of extralateral rights. This is a condition in both of the countries above named which has seemed to work no hardship upon any one, and certainly the limitation of underground rights by vertical planes through all lines makes a locator's rights clear. In view of the long and costly litigation which has involved so seriously many of our most important mining districts, it would seem to be the part of wisdom to avoid a repetition of similar trouble on titles of lode mining claims, by the enactment' of a law similar to that in force in British Columbia. Objections have been raised by .representatives of English companies to the investment of large amounts of money in mining operations in the United States, because of the insecurity of title under the 'present apex law; and the statement has been made to me personally by one of the largest English operators, that he would .never again consent to the purchase of mines in the United States, preferring Mexico with all its revolutionary troubles to the danger of encroachment upon his underground rights by an unscrupulous neighbor. Without going into further argument as to the desirability of the I(square location," it should be sufficient to say to those who are inclined to "let well enough alone" and still stick to the "law of the apex" that there have never been any serious objections raised to this feature of the square location in either British Columbia or Mexico. There are well founded and logical reasons for abandoning the doctrine of extra-lateral rights since it is so difficult of interpretation; the most natural substitute being a law similar to that of British Columbia, giving to each locator an area 1,500 ft. square. I would advocate the right to locate adjoining claims of equal extent on either side of the discovery claim, on the strike of the lode, subject to a seasonable requirement in the matter of work upon them; and in the case of a vein dipping flatter than 45' from the horizon, or in case of a

Jan 1, 1915

By C. A. Wert, M. G. Coleman

The Zener relaxation in alloys in the a! solid-solution region of the Cu-Ni-Zn ternary system has bear investigated. Of the binary solid solutions that bound this region, Cu-Zn and Ni-Zn exhibit measurable Zener peaks whereas Cu-Ni does not. At constant atomic percent copper, the Peak height drops uni.forinly from the value in the Cu-ZTL binary to zero in CIA-Ali. The cariation of peak ternperatuve with composition is linear. At constant atomic percent zinc, the peak height in the ternary alloys goes through a large maximum as compared with the binary values. The temperature of these peaks varies smoothly with composition. The half-width of the peaks in the ter nary alloys, however, are much larger than those in the binaries. A large enhancement of the relaxation strength of the Zener relaxation in ternary Au-Ag-Zn alloys as compared to the relaxation strengths in Au-Zn and Ag-Zn binary alloys was observed by Firson and ert.' Since this effect was unexpected, the present study was devised to investigate whether enhancement of the Zener relaxation in ternary alloys is a general feature or is particular to the Au-Ag-Zn system. We have chosen the Cu-Ni-Zn alloy system for this investigation. Measurable Zener relaxations are observed in both the Cu-Zn and the Ni-Zn binary systems, but not in the Cu-Ni binary system. A large solid-solution region extends to large concentrations of zinc, making it possible to vary composition of the alloys over a wide range without crossing phase boundaries. EXPERIMENTAL PROCEDURE Two series of alloys were prepared. the first at constant atomic percent copper, the second at constant atomic percent zinc. The compositions of these alloys are shown by the circles in Fig. 1. The alloys were prepared by melting the individual components, each of which had previously been vacuum-melted, in an evacuated quartz capsule in an induction furnace at 1500 C. The capsules containing the molten alloys were quenched in water to reduce coring. Any individual melt which exceeded 0.001 pct weight loss was discarded. The ingots were swaged to a 50 pct reduction of area and annealed for 1 week in an evacuated quartz capsule to aid homogenization. The alloys were then

Jan 1, 1967

By P. W. Davies, B. Wilshire

PREVIOUS investigations on the effect of stress changes on the high-temperature creep and fracture behavior of metals have been confined mainly to the testing of complex alloys.172 Most of these alloys are structurally unstable during creep because of such effects as recrystallization, overaging, and so forth, so that the results are of limited application. The only pure metals on which observations have been made appear to be lead3,4 and aluminum5 tested under conditions which allow rapid recovery to take place. The present work describes the effect of a single stress change on the creep and fracture properties of a metal in which recovery is very slow. A Ni 0.1 at. pct Pd alloy was used so that grain growth and recrystallization did not occur during creep testing. Specimens of this material were heat-treated to give a uniform grain size of 10 grains per mm. Creep tests were carried out at 500°C using Denison T.47 machines; details of the creep-testing procedure have been given elsewhere.' All specimens were tested at a constant initial stress of 5 tpsi which gives, in an uninterrupted test, a minimum creep rate of ~10-3 pct per rnin and a life of -7000 min. Specimens were loaded under these standard conditions and after 1500 min, when secondary creep was well-established, the stress was changed to either 8, 7, 6, 4, 2, or 0 tpsi for a period of 180 min. After this time the original load was reapplied and the tests continued to fracture. The results are shown in Fig. 1. No detectable creep occurred during the period of reduced load, even at 4 tpsi, and on reverting to 5 tpsi the creep rate returned to its original value immediately. Increasing the stress to 8, 7, or 6 tpsi resulted in an instantaneous extension followed by a period of transient creep leading to a new steady creep rate. On returning from these higher stresses, the resulting creep rate at 5 tpsi was very low compared with the original value. Furthermore, the higher the stress during the stress change, the lower was the final creep rate. It is significant that the rupture life is comparatively unaffected by any of these stress changes.

Jan 1, 1965

By J. J. Frawley, W. J. Childs

PREVIOUS studies have shown that if a supercooled liquid metal was perturbed by vibration the probability of nucleation is is During a recent investi- gation to determine quantitatively the amount of energy needed to cause nucleation in a given supercooled liquid specimen, it was found that at low-energy values in the megacycle range, below the threshold energy value for cavitation, the amount of dynamic supercooling was greater than the amount of static supercooling. That is, if a specimen had a given amount of thermal supercooling under static conditions, its thermal supercooling could be increased by the addition of low-energy sound waves. The material used in this investigation was high-purity bismuth. This material was chosen because of its low melting point and the high degree of supercooling which could be easily obtained. The sound gener- ator employed in this work was a commercially built Sperry ultrasonic testing unit. This unit was equipped with a barium titanate crystal as a piezoelectric transducer. These sound waves were transmitted to the supercooled melt by a Pyrex rod, as shown in Fig. 1. The transducer was coupled to this Pyrex rod wave carrier by motor oil. The Pyrex wave carrier was approximately 1.5 ft long to prevent damage to the transducer by heat. The diameter of the Pyrex wave carrier appears to be critical. In the initial tests a wave carrier of 0.5 in. in diam was employed. However, the sound waves had no effect on the amount of dynamic supercooling. When the diameter of the wave carrier was increased to approximately the inside diameter of the Pyrex crucible, the sound waves were more effective. Approximately 200 g of metal was melted under a stannous chloride flux in a 30-ml beaker by induction heating. The temperature was recorded by a Pyrex-encapsulated chromel-alumel thermocoule which was placed in the beaker after the bismuth melted. The Pyrex wave carrier was immersed slightly below the surface of the liquid bismuth and the specimen was reheated to about 500°C. It was observed that the amount of supercooling depends on the amount of superheating the specimen receives; therefore, for meaningful results the amount of superheating was the same for all heating cycles. The specimen was allowed to cool in air and the change in temperature was continuously monitored with a potentiometric strip-chart recorder.

Jan 1, 1969

By Bailey Willis

IN 1882, Peckham put forward a provisional hypothesis to account .or the distillation of petroleum.1 He did not formally state the hypothesis, but in a discussion of facts drawn from many fields he made it clear that he regarded petroleum, and especially the petroleum of the Pennsylvania fields, as a "fractional distillate produced under high pressure and consequently at a comparatively high temperature.?2 He quotes James Hall on the geology of the Appalachians and says:3 It is not necessary here to discuss the nature or origin of metamorphic action. It is sufficient for our purpose to know that from the upper Silurian to the close of the Carboniferous periods the currents of the primeval ocean were transporting sediments, sorting them into gravel, sand, and clay, forming gravel bars and great sand beds beneath the riffles and clay banks in still water, burying vast accumulations of sea weeds and sea animals far beneath the surface. The alteration, due to the combined action of heat, steam, and pressure, of the formations of the Appalachian system from Point Gaspe in Canada to Lookout mountain in Tennessee, involving the Carboniferous and earlier strata, distorting and folding them, and converting the coal into anthracite and the clays into schists along their eastern border, could not have ceased to act westward along an arbitrary line, but must have gradually died out farther and farther from the surface (source?). The great beds of shale and limestone containing fucoids, animal remains, and even indigenous petroleum must have been invaded by this heat action to a greater or less degree, and that "chronic evaporation" of Prof. Lesley must have been the inevitable consequence. From an investigation of the relations between coal and petroleum, White has" more recently concluded as follows: (1) Petroleum is a product generated in the course of the geodynamic alteration of deposits of organic debris of certain types buried in the sedimentary strata. (2) The quantity and characters of the oils generated are determined by: (a) the composition of the organic deposit at the beginning of its dynamo-chemical alteration; (b) by the stage in the progress of the dynamo-chemical alteration of the organic substances; (c) by the elimination, under certain conditions, of the heavier and more' viscous hydrocarbons through filtration incident to migration.

Jan 1, 1920

By S. H. Davis

The pyrites used in making sulfuric acid in the United States have been largely imported from Spain and Canada, the Spanish imports amounting to nearly 1,000,000 tons per annum in the pre-war period. The greatly increased use of sulfuric acid and the cutting off of these Spanish imports, incident to war conditions, brought about a threatened shortage of sulfur supplies during the war period. The bituminous-coal mines of ccrtain districts have, for many years, furnished a small tonnage of pyrite in the form of coal brasses. A mechanical concentrator at Danville, Ill., for a number of years, has been treating hand-picked lump pyrite and coal from the picking belt and from the mines and a small plant near Gillespie, Ill., for a few months has been recovering pyrite from washery refuse. Many mines throughout Illinois, Indiana, Western Kentucky, Ohio, and Pennsylvania have shipped an occasional car of the hand-cleaned lump pyrite. Only a very small percentage of the available pyrite has been recovered in this way, however, as usually the miners throw such lumps into the gob with slate and other impurities. It has been estimated that the western Indiana coal field could furnish more than 100,000 tons of pyrite per annum. The present production is very small. The possibility of furnishing the domestic trade with pyrites recovered as a byproduct from coal-mining operations appears attractive but there are certain features difficult to overcome. Pyrite, to be used in acid making, must meet with certain requirements as to size and purity. Lump ore for grate burners should be under 3 in. (7.6 cm.) and over 1 in. (2.5 cm.) in diameter. Fines for use in mechanical roasters should be under quarter mesh. The material should be high in sulfur, free from arsenic and phosphorus, and as low in carbon as possible. The pyrite obtained from coal can be made to meet all the above requirements, but it is difficult to remove all the carbon. The pyrite in coal occurs as bands and nodules of varying thickness and size and of comparative purity, but mixed with this is more or less web sulfur. The web sulfur carries admixed coal, which may make the concentrate run up to several per cent. carbon. This makes the concentrates subject to firing, causes heavy consumption of niter, and lowers the acid-plant capacity, due to dilution of gases. The hand-cleaning methods

Jan 1, 1920

By D. D. Button, L. D. Jaffee

INTEREST in the use of graphite as a high-temperature engineering structural material has recently increased markedly. However, actual use of this material has been limited, in part because information about its high-temperature mechanical properties has been lacking. The information needed includes not only reliable values for the properties, but also how to control these properties. Malmstrom, Keen, and Greenl have reported on the tensile and creep properties of some graphites above 2700° F (1500°C). They observed measurable creep under tensile loading at 4000 OF (2200 °C) and higher, with elongations of about 7 pct at 4500°F. Their typical elongation-vs-time curve showed the normal three stages of creep found for many metals at elevated temperatures. The specimens used were heated by passing an electric current through them. This method of heating caused a significant difference between the surface and axis temperatures, and may have affected the results. More recent work by kattus, in which the specfinens were also heated by their own resistance, showed very little plastic deformation for either slow or fast tensile testing or for creep testing. Work at this Laboratory, already reported,3 showed that for temperatures above 4500 "F and under conditions of slow tensile loading some commercial graphites exhibited elongations up to 20 pct. The work reported here is the continuation of a study of the tensile creep behavior of some commercially available synthetic graphites at temperatures up to 5300°F, and is preliminary to a more systematic investigation of the variables governing the high-temperature mechanical properties of graphite. MATERIALS TESTED The tests were conducted on six blocks from four lots of synthetic graphite bearing four different commercial-grade designations. These blocks were selected because their tensile stress—strain properties had been determined in previous work.3 Table I pre- sents the available information, supplied by the producers, on the processing of these materials. Also included in this Table are the densities and the tensile strengths at room temperature and 4500°F determined by the authors. EXPERIMENTAL TECHNIQUE The furnace used to heat the specimens for testing is shown in Fig. 1. The heating element was a graphite tube, 3-in. OD by 2 1/2 in. ID by 24 in. length. A spiral was cut into the 6-in. center portion of this tube to provide a high-resistance sec-

Jan 1, 1961

By C. H. Frick

Before presenting the main topic, as indicated by the title, this paper will give some of the high-spot history of the anthracite industry. Introduction The earliest recorded use of anthracite was in the year 1762, when a company of Connecticut pioneers discovered anthracite near the present city of Wilkes-Barre, Pennsylvania. In the early days of the industry, the coal was used only in large pieces, the smaller pieces being discarded to waste piles. As the output of the industry increased during the nineteenth century, uses were developed for somewhat smaller sizes down to and including pea coal. Early in the twentieth century, sizes smaller than pea, such as No. I and No. 2 buckwheat, were developed and used. Accumulations of piles from current mining operations were still increasing; that is, the smaller sizes were still being discarded. It was not until after World War I that preparation of the so-called steam sizes began commercially. This was largely No. 3 buckwheat, which is screened through a 3/16-in. round-hole screen and over a 3/32-in. or a 1/16-in. round-hole screen. Use of Smaller Sizes The earliest recorded experience in burning the small sizes of anthracite for steam production, other than in a previous small experiment, was in the year 1913, when a size known as "boiler fuel" was introduced—a mixture of rice and barley (No. 2 and No. 3 buckwheat). At that time, there was still no method known for burning the still smaller sizes. At the present time, various sizes down to and including No. 5 buckwheat are being prepared (Table I) from current mining and bank-reclaiming operations. The sizes of No. 4 and No. 5 buckwheat and smaller are generally being used for steam production in large boilers. The Pennsylvania Power and Light Co., following World War I, used 680,000 tons of anthracite per year, burned largely on stokers for production of steam, whereas for the year 1943 it used 1,940,000 tons of stoker sizes and 400,000 tons of smaller sizes for grinding and burning in pulverized form. This company has taken a very large part in the research and development of ways and means of burning these smaller sizes of anthracite, including the grinding of the very small sizes. This paper is particularly concerned with the latter feature.

Jan 1, 1949

By D. W. Fuerstenau, J. H. Brown

The paper by Professors Sun and Mitchell illustrates the value of ultrasonics as a tool for the mineral engineer. In particular, it opens up a number of possibilities to those interested in the field of comminution. The provision of desliming technique, which is thorough as well as rapid, is a distinct contribution, but the data of the paper suggest applications beyond desliming, in that the same treatments may be useful for size determination purposes. Fig. 1 shows that a marked dependence exists between particle size and the height to which it can be elevated by ultrasonic vibrations. While the curves are only extended down to a size of about 100 u, the fact that they appear to be increasing in slope in this range suggests that the separation may be even more marked here. This, we feel, is very strong evidence that a nlethod for fine sizing could be developed to use ultrasonic waves as the separating force. Professors Sun and Mitchell indicate that floccula-ti~n will present no difficulty: "During the investigation it was found that ultrasonic waves were able to dislodge the adhering gangue particles from the min- era1 surfaces and to disintegrate the soft particles into fine sizes." Thus, it appears that the use of ultrasonic waves as the power behind a size separation process may eliminate the problem of flocculation encountered in most wet sizing techniques. It would be interesting to size a fine material under conditions in which particles are known to be flocculated and under conditions where they are known to be dispersed. Use of a sizing technique of this nature may solve several problems that have long persisted in the fine sizing field. The flocculation problem may be overcome; the continuous production of closely sized fractions may be possible with a device similar to the one described; and with photoelectric methods, rapid analyses in the subsieve sizes may be possible. In general, we suggest that this paper be followed by a study of the sizing applications of the apparatus described. We feel that such a study would not only be rewarding in providing a new sizing technique, but also that the present paper almost requires such work to complete the picture of particle motion in a field of ultrasonic waves.

Jan 1, 1958

By Nathaniel Arbiter, Arthur F. Taggart

THE chemical reaction occurring in collection of nonmetallic minerals with amine-type collectors was early postulated by students of flotation phenomena to be metathesis between the mineral and the collector, involving exchange between the amine-bearing (aminium) ion and the cation of the mineral, and formation at the mineral surface of an oriented film of the amine salt of the mineral anion. Qualitative evidence of exchange has been obtained on several occasions at Columbia. Thus 1000 c.c. of a solution containing 495 mg. of laurylamine hydrochloride was shaken 17 min. with 100 grams of barite and ground in a porcelain mill to pass a 200-mesh screen; the mixture was then set aside for 48 hr. Filtrate therefrom analyzed 476 mg. per liter of laurylamine hydrochloride. There was no substantial loss of chloride ion (78.4 mg. per liter in the original; 74 in the filtrate). No successful analyses were concluded for barium ion. Earlier, confessedly rough work with scheelite indicated a solution gain in Ca++ equivalent to about one-half the aminium ion lost. Real quantitative proof of the exchange, in the form of an established stoichiometric balance, is unknown to the authors. The data of the present paper, however, obtained from experiments designed on the basis of the exchange hypothesis, constitute strong evidence of its truth, and at the same time point the way to economic utilization of the expensive nitrogen-bearing collectors in concentration of the low-priced nonmetallic minerals. The basic postulate underlying the experiments performed was that, if the collecting reaction is of the type [R+ + Y- + MX =± RX + M+ + Y¬] where R = aminium ion, Y = the anion of the amine salt, and M and X are, respectively, the cation and anion of the mineral, the reaction should obey qualitatively the implications of the massaction and solubility-product laws. This is to say that coating and collection should be aided by the addition to the solution of either ion (R+ or X-) of the collector-coating compound, and hindered by the addition of either of the ions M+ or Y-. Experimental work comprised determination of (1) the relative solubilities of the laurylammonium salts of a variety of nonmetallic-mineral anions; and (2) the contact angles1 of various minerals in solutions containing different concentrations of the postulated controlling ions. Semiquantitative flotation tests were run with barite as checks on the diagnostic character of the contact angles. The amine

Jan 1, 1944

By A. G. Loomis

IT is only within the past 10 years that serious attempt appears to have been made to improve rotary drilling fluids by the application of the principles of colloid chemistry, although the use of chemicals to control the rheological properties of clay slips has long been known in the ceramic industry. The main difficulty apparently lay in the lack of a complete analysis of all of the functions of a drilling fluid in the drilling of the well, together with the lack of adequate consideration of how colloid science could be applied to secure these ends, and particularly how apparent antithetical properties of the fluid could be compromised. Thus one analysis1 of the many requirements of a drilling fluid proved conclusively that the viscosity should be low, in order that cuttings and entrained gas might be eliminated effi-ciently in the settling ditch, while the loss in carrying capacity accompanying low viscosity could be regained by increasing either the density of the mud or the upward velocity of the mud stream in the annular space of the well, and the danger of sticking of the drill stem due to rapid settling in case of enforced suspension of drilling operations could be eliminated by enhancing the thixotropic properties of the fluid. The desired properties of the drilling fluid having thus been established, it was a natural step to treat the fluid with vis-cosity-reducing chemicals, such as salts of weak organic acids1,2-for example, sodium tannate or gallate-and to adjust the pH to the alkaline side to such a degree of thixo-tropy as would give low viscosity and low yield point under the conditions of flow prevailing in the settling ditch, but rapid gelation and high yield point when quiescent in the annular space during shut-downs. In fact, flow in the settling ditch should be just short of turbulent while flow in the well, together with the flow of mud past the cuttings, is practically always turbulent. The use of chemicals other than those mentioned, such as Calgon (sodium hexametaphosphate) and certain other phosphates together with sodium tannate, has now become standard practice and it is the consensus that this method of treatment has proved to be an important step in the development of the art of drilling oil wells.

Jan 1, 1940

By D. J. Carney, R. L. Stephenson

A sampling technique has been developed for procuring a sample of sinter representative of the entire depth of the sintering bed. The sampling method involves the use of an open-bottom metal basket that rides on the grate of the sintering machine and when removed contains a sample of the sintered product. Additional data have been obtained to indicate that the tumbler test is a suitable means of measuring sinter strength. IN the last few years additional sintering facilities have been installed in both the Pittsburgh and the Chicago district of the United States Steel Co. Since the construction of these sintering plants made possible the use of higher percentages of flue-dust sinter in our blast-furnace burdens, it became important to study means of controlling the quality of sinter to obtain optimum results in the blast furnace. For controlling an operating process, it is necessary first to establish standards by which the quality of the product can be judged. For sinter, it appeared that an important property was its strength or its resistance to degradation during transportation and charging into the furnace. Consequently work was undertaken to establish a standard for sinter strength that could be used both for controlling sintering-plant operations and for correlating sinter quality with blast-furnace performance. The first problem in setting up a standard was that of procuring a sample that would be representative of the sinter made under any particular set of conditions at the sintering plant. Since the United States Steel Co. sintering plants discharge the finished sinter either into a large pit or onto a rotary cooler, the sinter becomes inseparably mixed with material sintered 2 hr before or 2 hr afterwards. For this reason the exact identity of the sinter is lost. A sample selected as the cooler is discharged, or as the sinter is removed from the pit, cannot be said to be truly representative of the sinter made at any specific time. Sampling The first attempt to procure a sample that would be representative of a specific sinter mix and of specific operating conditions was made by stopping the Dwight Lloyd sintering machine and removing an entire pallet full of sinter. This method, however, proved very difficult to perform and interfered considerably with the operation of the plant. To overcome this difficulty, a sampling method was devised by technologists at South Works enabling them to secure, without interrupting the sintering operation, a sample of about 1 cu ft of sinter, representative of sinter for the full depth of the sintering bed. The South Works method involves the use of a steel-frame-work basket. A typical basket is shown in Fig. 1. The basket has been used both with and without crossbars along the bottom. As long as the crossbars are in the same direction as the grate bars on the sintering machine they do not interfere with the sintering process. The basket is set on an empty grate of the Dwight Lloyd sintering machine before it passes under the swinging feed spout, see Fig. 2. When the basket is removed after it has travelled the length of the sintering machine, it contains the sample. Just before the basket is removed, the sinter is scored and chipped to facilitate removal of the sample from the sinter bed. A view of the basket after its removal is shown in Fig. 3. Although the sampling method was originally designed for use on a Dwight Lloyd sintering machine, it can also be used on the Greenawalt type of machine. When used on the Greenawalt-type machine, the basket is placed on the sintering grate before the charging car passes over it, and finally it is removed just before the pan is dumped. Testing After a method of obtaining a representative sample of sinter had been developed, the next step was to select a method of measuring its strength. The irregular shape and size of the sinter pieces precluded the use of a simple compression test for determining strength; consequently, the shatter test and tumbler test were investigated. To perform the shatter test, a sample of sinter, approximately 5 lb, is dropped from a hinged-bottom box at a height of 3 ft onto a steel plate. The broken sinter is sieve-analyzed after a specified number of drops. The tumbler test is performed with the use of a standard ASTM coke-tumbling drum. The drum is 3 ft in diam and is equipped with two lifter bars diametrically opposite one another on the inner periphery of the drum. The drum is rotated at a speed of 24 rpm for 200 revolutions, and after tumbling the sample is sieve-analyzed. To express as single numbers the results of sieve analyses after shattering or tumbling, the method suggested by R. E. Powers1 was employed. This method involved plotting the size of the sieve openings on a logarithmic scale and the cumulative per cent larger than each sieve on a probability scale as described by J. B. Austin.' By interpolating from the plotted data, which in most cases approximated

Jan 1, 1954

By P. S. Kotva

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

Jan 1, 1969

By W. F. Hosford, E. W. Kelley

Deformation studies have been conducted at room temperature on single crystals of magnesium and magnesium alloys with thorium and with lithium. Single crystals oriented to suppress shear on the easily activated basal slip systems were deformed by plane-strain compression. Compression along the C axis was accommodated by {1011} banding. Compression perpendicular to the unconstrained c axis activated {1012} twinning, and, after virtually complete twinning, deformation continued by {1011) banding in the twinned material. Compression perpendicular to the constrained c axis was accommodated by the simultaneous operation of (1012) twinning against the constraint and (1011 ) banding. Although this orientation was favorable for {1010)(1210) prism and {1011}(1~10) pyramidal slip, these modes were not observed in pure magnesium or in Mg-0.5 pct Th. However, {10i0)(1~10) prism slip was observed in crystals of Mg-4 pct Li during compression perpendicular to the constrained c axis. Fracture in all materials occurred parallel to (1124) or {l~il) depending on the orientation and composition of the specimen. THE mechanical behavior of the hcp metals is strongly anisotropic. Although several slip systems have been reported the slip is cpmmonly in the directions of closest packing, the (1210),' and this does not produce strains parallel to the c axis. Hence the inherent anisotropy. The deformation mode most easily activated in magnesium at room temperature is (0001)(1210)- basal slip. Also {1010}(1~10) prism slip and {1011)(1210) pyramidal slip have been reported, primarily at elevated temperatures.2"4 However, at room temperature the shear stresses to activate the prism and pyramidal modes are roughly a hundredfold greater than that required for basal slip.'j4 Thus prism and pyramidal slip may be expected only under special conditions of loading. Strains normal to the basal plane can be produced by twinning, however. Many twinning modes have been reported for magnesium,' with (1012) twinning the most common and relatively easy to activate. Magnesium can deform by (1012) twinning when stressed along the c axis jn tension, but not in compression. In contrast, (1011) twinning is activated by compression along the c axis and not by tension. In addition to primary twinning, secondary twinning or slip can occur within the reoriented material of primary twins.' In general at least five independent shear systems must be active to bring about an arbitrary shape change such as that in the individual grains of a deforming polycrystalline material.' Because basal slip can_ provide only two independent shear systems and (1012) twinning can only accommodate an extension of the c axis, other deformation modes must be active in magnesium for an arbitrary shape change to occur. The purpose of this investigation has therefore been to study the various deformation modes in magnesium at room temperature, with special emphasis on those modes that are less easily activated. The effect of the alloying elements, thorium and lithium, has also been investigated. In polycrystalline aggregates, unambiguous identification of deformation modes is extremely difficult and the direct evaluation of the resolved shear stresses to activate them is not feasible. On the other hand, uni-axial tension and compression experiments on single crystals may not activate some of the- deformation modes because basal slip and/or {1012) twinning cannot be suppressed in most orientations. However, it should be possible to activate all possible deformation modes using oriented single crystals and plane-strain compression. Identification of active deformation systems and evaluation of the resolved shear stresses required to activate them should be facilitated. Wonsiewicz and Backofen have recently completed an investigation of the plasticity of pure magnesium crystals at various temperatures utilizing plane-strain compression and selected crystal orientations. This technique has also been used in the present work. The seven orientations selected for study are indicated in Table I. Plane-strain compression along the c axis (orientations A and B) should activate some deformation mode _other than basal, prism, or pyramidal slip, or (1012) twinning. In orientations C and D, prism or pyramidal slip would be expected to take place. When the compressive load is applied perpendicular to an unconstrained c axis (orientations E and F) the three slip modes should be suppressed but not (10i2) twinning. In orientation G, basal slip should occur.

Jan 1, 1969

By G. Bruggeman, K. G. Kreider

Grain boundary dij]usion coefficienls were measured in tungsten between 1400° and 2200° C and can be expressed by the equation sq cm per sec This activation energy confirms some eavlier estimates made .from tungsten sintering experiments. Grain boundary diffusion was found to occur in sub-bozrndavies having -misorientations of less than 10 deg. The actiuation energy for this subboundavy diffusion is equal to that for dijjusion in incoherent grain boundaries with in the limits of error. This is shown to be consistent with the dislocation model of Low-angle boundaries wheve diffusion occlcvs along- the dislocation 'YPipes" comprising -tile boundary. RECENT investigations of the sintering of tungsten powders all report activation energies which are considerably less than the activation energy for tungsten volume diffusion. Kothari' reports a value of 100 * 5 kcal per mole, Hayden and Brophy' obtained 90 kcal per mole, and Vasilos and smith3 found 110.7 kcal per mole from their sintering studies. Since most determinations of the activation energy for volume diffu-sion4-' fall between 120 and 160 kcal per mole (the true value seems most likely to be nearer 150 kcal per mole), the conclusion is drawn that the mass transport leading to densification during sintering is accomplished by grain boundary diffusion. This interpretation is consistent with various diffusion models of the sintering process. 10-12 Vasilos and Smith calculate diffusion coefficients from their data which fit the equation D * 1.36 x 10* exp(-llO,700/HD However, no direct measurements of tungsten grain boundary diffusion have been made. Furthermore, considerable disagreement exists between the directly measured values of tungsten volume diffusion.'-' In order to corroborate the inferred results of the sintering experiments concerning grain boundary diffusion and to provide accurate diffusion data essential to the analysis of the kinetics of creep, oxidation, precipitation, and so forth, the present work was undertaken to measure self-diffusion in single-crystal and polycrystalline tungsten between 1400" and 2200°C. It is within this temperature range that tungsten sintering is done, the re crystallization of tungsten occurs, and the widest application of tungsten as a high-temperature material will probably be made. EXPERIMENTAL PROCEDURE Radioactive WlE5 was produced by irradiating tungstic acid in a neutron flux of 1.2 x 1012 neutrons per sq cm per sec for 36 hr. A 2-week waiting period was allowed for the decay of w"~ also produced by the irradiation. (w"~ has a half-life of 24 hr.) The half-life of the remaining isotope was determined to be 75 days confirming the presence of w lE5 and the absence of any undesired radionuclide. Specimens 4 in. in diam and $ in. thick were cut from polycrystalline swaged tungsten rods (recrystal-lized) and from Linde single-crystal rods. Chemical analyses of these materials appear in Table I. Actually upon closer examination, the single-crystal specimens were found to consist of several subgrains separated primarily by tilt boundaries in which the misor-ientation ranged from 3 to 10 deg. Thus, it was possible to measure boundary diffusion coefficients in these low-angle subboundaries as well as in the incoherent boundaries of the polycrystalline specimens. The two faces of each specimen were ground flat and parallel within 0.0001 in. The radioactive tungstic acid was dissolved in concentrated ammonium hydroxide, placed on the ground flat of the specimen, and evaporated to dryness. The oxide was then reduced in hydrogen at 1000°C resulting in a layer of wlE5 approximately 1 p thick. The diffusion anneals were performed in vacuum in a tantalum resistance furnace. Time at temperature ranged from 10 hr at 1400°C to 2 hr at 2200°C. The penetration profile was determined by measuring the residual activity after successive removal of surface layers by grinding on metallographic polishing paper. Extreme care was exercised to insure that sections were always taken normal to the diffusion direction; this was verified repeatedly by checking that front and back surfaces of the specimen remained parallel. The activity was measured with an end-window Geiger-Mueller counter. The sides and edges of the specimen were well-shielded to eliminate possible effects due to surface diffusion. The weight of the

Jan 1, 1968

By R. H. Olds, B. H. Sage

The transient flow of gases in long pipe lines is a problem of industrial interest. The present discussion deals with the application of the conservation of momentum and material to the transient flow of gas in conduits which are long with respect to their diameter. Solutions of the resulting equations include consideration of variations in friction and specific volume of the fluid as functions of time and position along the conduit. The changes in state along the pipe line are established as a function of time. The methods proposed may be extended to other situations. The flow of compressible fluids under steady conditions' has been considered in detail. Primary emphasis was placed on the development of simple means of taking into account the non-uniform flow' realized in long conduits under such conditions. Binder2 discussed the essential differences between the flow of compressible and uoncompressible fluids. Bonilla" proposed direct methods of solution for equations describing isothermal flow in long pipes. Similar considerations limited to steady flow have been discussed by Ruth.' Palsgrove 5 sugrested a graphical means of solving specific problems relating to the flow of gases in conduits of uniform section. Some of the basic concepts of the flow of a compressible viscous fluid in straight tubes have been described by Kuo.6 Problems of this type require knowledge of the equation of state of the fluid. In many cases it liar been convenient to assume that the fluid follows the relationship ascribed to a perfect gas. The treatment of unsteady flow of compressible fluids is less complete. This state of affairs result* from the fact that the differential equations relating pressure and flow rate with time and position for unsteady flow are nonlinear in character.' Muskat and Wyckoff presented an excellent treatment of the situation in laminar Bow where inertia forces were not of controlling importance. Somewhat earlier Hurst9 discussed the uncteady flow of fluids in petroleum reservoirs. Helhering-ton. MarRoberts. and Huntington'" established experimentally the pressure distribution and accumulative flow rate of natural gas through an unconsolidated sand. Recently Joffe11,12 conhitlcretl the specific problem of the flow of natural gas in relatively long.,. pipe lines for unsteady conditions with emphasis upon the economic feusibility of the storage of gas in such a reservoir. These discussions were based upon approximations of the partial differential equations applying to the condititons of flow. The results were descriptive of the physical situation and indirated the effertiveness of large pipe lines as cyclic storage facilities for natural gas. The advent of analog computers" has increased materially the practicality of solving nonlinear partial differential expressions. Several iterative numerical and graphical methods14,15,16 have been developed to solve nonlinear equations. However, it appears that the pair of simultaneous nonlinear partial differential equations involved in problems of this nature are not directly susceptible to solution by presently available analog computer or formal iterative numerical techniques. Nevertheless. graphical analyses afford a means of obtaining data of engineering value without special equipment. MATHEMATICAL CONSIDERATIONS Since the length of the conduit is large in comparison to the cross section in the cases to be considered, it is possible to treat the characteristics of the flow as independent of position in the cross section of the conduit. This possibility follows since the energy- connected with the velocity profile is small compared to that required to overcome the friction associated with its movement throughout the length of the line. Average values of the pressure. velocity. kinetic energy. momentum, and specific volume may he assigned to the fluid at any particular cross section. From a mathematical viewpoint this may be expressed in the following way for velocity: µ = µ(?X)..........(1) The uncertainties introduced by such assumptions usually are negligible when the ratio of length to diameter is greater than the order of 1.000. On this basis a volume element ma!. be considered to occupy the entire cross section of the conduit. Such an element is presented in Fig. 1.

Jan 1, 1951

By R. H. Olds, B. H. Sage

The transient flow of gases in long pipe lines is a problem of industrial interest. The present discussion deals with the application of the conservation of momentum and material to the transient flow of gas in conduits which are long with respect to their diameter. Solutions of the resulting equations include consideration of variations in friction and specific volume of the fluid as functions of time and position along the conduit. The changes in state along the pipe line are established as a function of time. The methods proposed may be extended to other situations. The flow of compressible fluids under steady conditions' has been considered in detail. Primary emphasis was placed on the development of simple means of taking into account the non-uniform flow' realized in long conduits under such conditions. Binder2 discussed the essential differences between the flow of compressible and uoncompressible fluids. Bonilla" proposed direct methods of solution for equations describing isothermal flow in long pipes. Similar considerations limited to steady flow have been discussed by Ruth.' Palsgrove 5 sugrested a graphical means of solving specific problems relating to the flow of gases in conduits of uniform section. Some of the basic concepts of the flow of a compressible viscous fluid in straight tubes have been described by Kuo.6 Problems of this type require knowledge of the equation of state of the fluid. In many cases it liar been convenient to assume that the fluid follows the relationship ascribed to a perfect gas. The treatment of unsteady flow of compressible fluids is less complete. This state of affairs result* from the fact that the differential equations relating pressure and flow rate with time and position for unsteady flow are nonlinear in character.' Muskat and Wyckoff presented an excellent treatment of the situation in laminar Bow where inertia forces were not of controlling importance. Somewhat earlier Hurst9 discussed the uncteady flow of fluids in petroleum reservoirs. Helhering-ton. MarRoberts. and Huntington'" established experimentally the pressure distribution and accumulative flow rate of natural gas through an unconsolidated sand. Recently Joffe11,12 conhitlcretl the specific problem of the flow of natural gas in relatively long.,. pipe lines for unsteady conditions with emphasis upon the economic feusibility of the storage of gas in such a reservoir. These discussions were based upon approximations of the partial differential equations applying to the condititons of flow. The results were descriptive of the physical situation and indirated the effertiveness of large pipe lines as cyclic storage facilities for natural gas. The advent of analog computers" has increased materially the practicality of solving nonlinear partial differential expressions. Several iterative numerical and graphical methods14,15,16 have been developed to solve nonlinear equations. However, it appears that the pair of simultaneous nonlinear partial differential equations involved in problems of this nature are not directly susceptible to solution by presently available analog computer or formal iterative numerical techniques. Nevertheless. graphical analyses afford a means of obtaining data of engineering value without special equipment. MATHEMATICAL CONSIDERATIONS Since the length of the conduit is large in comparison to the cross section in the cases to be considered, it is possible to treat the characteristics of the flow as independent of position in the cross section of the conduit. This possibility follows since the energy- connected with the velocity profile is small compared to that required to overcome the friction associated with its movement throughout the length of the line. Average values of the pressure. velocity. kinetic energy. momentum, and specific volume may he assigned to the fluid at any particular cross section. From a mathematical viewpoint this may be expressed in the following way for velocity: µ = µ(?X)..........(1) The uncertainties introduced by such assumptions usually are negligible when the ratio of length to diameter is greater than the order of 1.000. On this basis a volume element ma!. be considered to occupy the entire cross section of the conduit. Such an element is presented in Fig. 1.

Jan 1, 1951

By Reynold Q. Shotts

CHEMICAL methods, based on the relative rates of oxidation of fusain, bright coal, and dull coal by nitric acid, have been devised to determine these coal components.1-4 Results obtained by oxidation methods for fusain have been checked against results obtained from microscopic methods5, 6on duplicate samples of the same coals, but to the author's knowledge this has not been done for bright and dull coal components. For this reason it is not certain that the two methods of analysis identify essentially the same chemical or physical units. It would be highly desirable to see results of the application of both methods to duplicate samples, but in the absence of any such data the author has attacked the problem indirectly. From the U. S. Bureau of Mines samples were obtained of three Alabama coals which the USBM had analyzed optically and reported on over the past 30 years. These samples were subjected to analyses by oxidation rate methods. Results of this work, and comparisons with the USBM analyses, have been published." This was the first indirect approach to the problem. The present report attempts a second indirect approach by way of internal validation. By nitric oxidation samples of two whole coals were carefully analyzed for fusain, bright coal, and dull coal. One coal was analyzed in duplicate. Duplicate portions of each of the coals were divided into three density fractions by means of heavy liquids. A duplicate portion of one of the coals was divided by sieving into three size fractions. Each fraction was analyzed by oxidation and its percentage composition calculated in terms of fusain, bright coal, and dull coal. Because the weight percent of each fraction was known, a material balance calculation for the whole coal was also made. The resulting reconstituted analysis of the whole coal could be compared to that determined by direct analysis. In addition, specific reaction rate constants were determined for each component and for each whole coal or fraction. Arbitrary reactivity indexes were calculated by dividing by 100 the sum of the products of the percent of each component in the coal and its specific reaction rate constant. The resulting figure was an average reactivity index for each coal or fraction. Weighting the reactivity indexes for each fraction by the percent of the fraction in the coal gave a reactivity index for each whole coal which could be compared to that calculated directly from the whole coal analysis. If oxidation analyses really delineate definite physical entities within the coal, or even definite groups of similar entities, reconstituted analyses calculated from fraction analyses should check closely those made of the whole coal. It probably is true that optical methods identify and describe a greater variety of components than do chemical methods and that variations are wide in the appearance and quantity of those components identified optically. Chemical methods based upon differences in oxidation reaction rates would of necessity be less discriminating, as between similar components, than would optical methods. The procedures followed for oxidizing the samples, analyzing the residues, plotting and calculating the percentage of each component, and calculating its specific reaction rate constant have been fully described.'-' In brief the method originally proposed by Fuchs et al.1 for the determination of fusain consists of the oxidation of small samples of coal in boiling 8N nitric acid in a condenser-fitted flask. After boiling for periods of 1/2 to 4 hr, the unoxidized residue is filtered and washed. The washed residue is treated with normal sodium hydroxide, diluted, and allowed to stand for several hours. The resulting brown liquor is removed, and the filtered residue dried, weighed, ignited, and weighed again. The ash-free residue is expressed as a percent of original dry, ash-free coal. The percent residue is plotted against time, and the extrapolation of this line to zero time gives the percentage of dry ash-free fusain present in the original sample. The shape of the resulting time plots has been explained' by the assumption that they are the result of two different types of reaction, the first part representing a first order reaction with rate a func-

Jan 1, 1956