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By J. Chupak, D. J. Salley, G. L. Simard

DITHIOPHOSPHATES and xanthates are the principal collectors for sulphide minerals, and consequently any knowledge of mineral-collector systems of this type is of value. In the present investigation an attempt was made to obtain information on the interaction of a typical dithiophosphate with galena. In carrying out this study, radioiso-topes, so much discussed in the past few years,', ' were extensively employed. By using radioactive dithiophosphate synthesized from radioactive phosphorus, a rapid and sensitive analytical procedure G. L. SIMARD is in the Research Division, Stamford Research Labs., American Cyanamid Co., Stamford, Conn.; J. CHUPAK, formerly in the Research Division, Stamford Research Labs., is now at Camp Detrick, Frederick, Md.; and D. J. SALLEY is in the Research Division, Stamford Research Labs. AlME New York Meeting, Feb. 1950. TP 2815 B. Discussion (2 copies) may be sent to Transactions AlME before April 30, 1950. Manuscript received Oct. 17, 1949. was at hand. This permitted determination of such important quantities as the rate of uptake of dithiophosphate by the mineral, the amount existing at equilibrium on the mineral surface and in the solution, and the desorption of the agent from the surface. Such measurements were possible even on single crystals of galena. In addition the exchange of dithiophosphate between the solution and the sorbed phase was examined, a matter which could be accomplished only by the use of isotopes. It is desired to point out at this time that throughout this paper the term "sorption" has been employed to designate the uptake of agent by mineral, without implication as to the nature of the process by which the uptake was accomplished. Experimental Materials: Galena: The galena was from the Tri-State district. For studies on ground mineral four preparations were used during the course of the investigation. These were prepared from selected large crystals by wet grinding in order to reduce surface oxidation. Alcohol was chosen as a convenient medium for this purpose. The ground mineral was then fractionated by sedimentation in alcohol, dried by evacuation, and stored in a nitrogen-filled desiccator. Data on the preparations are tabulated in table I. The size analysis indicated that the areas of the preparations were of comparable magnitude, even though the absolute values may be somewhat incorrect. Dithiophosphates: Nonradioactive dithiophbsphate (di-isopropyl or di-secondary butyl) was obtained by purification of a commercial product. An aqueous acid solution of the agent was extracted with petroleum ether, the ether layer dried, and the dithiophosphate precipitated as ammonium salt with anhydrous ammonia. Several repetitions of this process resulted in a nearly colorless, flaky product of good purity. (General formula (RO,)PSSNH,). Radioactive dithiophosphate was synthesized by heating radioactive elementary red phosphorus* • For early experiments (1943 to 1944), the elementary red phosphorus was obtained from the cyclotron group at the Crocker Radiation Laboratory of the University of California. Berkeley, through the courtesy of Dr. Joseph W. Hamilton. For more recent work (1946 to 1949). the elementary radioactive Phosphorus has been supplied by the Oak Ridge National Labarotories on allocation from the U. S. Atomic Energy Commission. with sulphur at 270" to 300°C to produce radioactive P,S,. The latter was then treated with the desired purified alcohol (isopropyl or secondary butyl) at 60" to 80°C to form the dithiophosphoric acid derivative. Purification was effected in the same manner as for the nonradioactive material. The effectiveness of the purification method was established by the isotopic dilution method." The same technique was used to show that only negligible decomposition of neutral or of carbonate solutions of the dithiophosphate took place over a period of a day; this was true whether or not galena was suspended in the solutions. Procedures: Radioactivity: The activity of a solution was obtained by counting with a small glass-jacketed, silvered Geiger counter, using a conventional scaling circuit.' Crystals and other solids were counted under a bell-shaped, mica-window counter tube. Sufficient counts were made so that the probable error of counting was of the order of +I-3 pct. The specific activity in terms of counts per minute

Jan 1, 1951

By Cloyd M. Smith

A few years ago, the Ventilation Committee established the practice of resenting one topic each year for discussion at the annual meeting. The practice has met good response on the part of committee members and I suggest that it be continued. The topic chosen for this year, "Underground Anemometry," is a topic which has bothered me for more than 20 years. It seems to me that the coal industry is content to rely on slipshod methods for measuring the rate of flow of air underground, so I prefaced my discussional charge to committee members with the statement that I regard air measnrements made in the usual way, with hand held anemometer, as no good. Agreements and disagreements came in from more than a dozen engineers, some of whom are with operating companies, coal and metal; some with manufacturers; others with government agencies. The statement was accompanied by a questionnaire on the use of the rotating vane anemometer and by one describing two methods of using a mechanically held anemometer. The questionnaire will be considered first. The questionnaire and statement are as shown on pages 5 and 6, the committee members and respondents are given on page 4, and the general comments of the latter on page 5. Questionnaire 1. Has your company or agency issued written instructions for care and use of anemometers? If so, please enclose a copy with reply. Only one answer, McElroy's, was affirmative. It gave reference to Bureau of Mines publications1'5 which recom- mend the hand held anemometer for rough measurements and indicate that am accuracy of 5 pct can be had if calibration and method factors are used. Mathews said that instructions are principally oral while Maize reported that state inspectors of his department are well trained in use and care of anemometers. 2. Are your anemometers calibrated periodically? If so, by their manufacturer? or by? Are calibralion corrections applied to all observed mean velocity readings? Only one respondent, Lee, answered negatively as to calibration. This means that anemometers are generally calibrated but the questionnaire failed to ask how often this is done. As no one volunteered the information, we have no data on this point. In six cases the instruments are sent to their manufacturers for calibration. but Krickovic reports that his company limits manu-facturers' calibrations to anemometers which are used by operating personnel; those used by the engineering department being calibrated by U. S. Bureau of Standards. The Anaconda Copper Mining Co. has its ventilation engineers calibrate its anemometers. Most of the respondents say that a calibration correction is applied to each mean velocity reading, but Krickovic limits this to surveys made by the engineering department. Since Lee does not calibrate, he has no correction to apply. Maize reports that his department has its anemometers calibrated but does not apply corrections. 3. Do your men hold the anemometer by hand in measuring air flow? for 1 min? or traverse the section? for 1 min? or at? points for 5 sec each? Of 10 replies, 6 were "yes," 3 were "no," and one was "seldom" with respect to holding by hand. Among the six hand holders, four hold in a central position in the measuring section for a minute, except that two of them, Krickovic and Matthews, traverse the section by hand for survey or fan test. Their operating personnel hold by hand, centrally, for routine measurements. McElroy sometimes traverses with hand-held anemometer in rapid survey work. 4. If the anemometer is not held by hand, how is it supported? Augustadt supports the anemometer on an adjustable rod, Condon on "a rod of sufficient length to reach all points with observer standing in one position throughout traverse and at arm's length from plane of traverse." I presume that arm's length must be interpreted liberally enough to allow for arm movement, otherwise it would be impossible to manipulate the anemometer throughout the traverse section. Mancha upholds Condon in this method of traversing. Glanville hangs the anemometer on the end of a 4-ft staff by the hasp at the top of the anemometer frame. McElroy mounts it on the end of a rigid square shaft, 12 in. long, the staff being at right angles to the axis of the instrument. He traverses the section in two halves, holding the anemometer 3 feet from his body.

Jan 1, 1950

By Edward H. Robie

PROBABLY nowhere in the United States or its possessions is mining development more active at present than in the Philippine Islands. Only a few years ago only one company was of any importance, the Benguet Consolidated. Now, five companies are paying dividends, five others have reached the producing stage, some seven others may produce this year, and a score or so are being actively developed. Gold production in 1933 was valued at about $8,000,000, last year at about $11,000,000, and this year an output valued at about $17,000,000 is envisaged. At the beginning of 1934 about 1750 tons of ore was being milled daily; at the end of the year, the tonnage was approximately 3400. In 1933 there were only thirteen Institute members in the Philippines; a year ago there were 27, and now there are 46. About fifteen thousand amen were employed in the mining industry last year, with mine payrolls amounting to $3,500,000. An immense amount of new machinery has been required. One difficulty has so far hindered gold-mine development to some extent-lack of adequate power. Each company therefore finds it necessary to generate its own power, and for this purpose diesel engines are generally adopted.

Jan 1, 1935

By Walter W. Bradley, OLAF P. JENKINS

IN April of this year the California State Division of Mines (formerly known as the State Mining Bureau) observed its 50th anniversary. The Division serves as a bureau of information and, an encyclopaedia of California's economic minerals. Its primary function is to make economic surveys of the mineral resources of California, their development and utilization. Geological studies also constitute a related part of the work as being necessary in tracing and out- lining ore deposits and the most likely areas in which to find them. The results of the Bureau's data-gathering are published in the form of annual reports of the State Mineralogist, and in bulletins on specific substances. The Division is just completing a series of reports on the mineral resources of the State arranged by counties.. It is now starting .a new series of reports arranged according to substances particularly the so-called non- metallic commercial groups. Of these the following are now available: clays, barite, and mineral paint. These will be followed by reports on feldspar and silica, diatomaceous earth, limestone and others

Jan 1, 1930

By Max Kraut

UNTIL VERY RECENTLY the flotation process has not found much application in the treatment of gold ores. No appreciable improvement has been made lately in the technology of this application; but the possibilities of flotation have been more fully appreciated. Excellent results were obtained long ago, but few operators paid much attention to them. For instance, in 1915 extensive experiments were carried out by Mr. Beauchamp and Minerals Separation on ores from the Dutch-Sweeney mine near Jimtown, Calif. The ore contained gold-bearing pyrite and laboratory tests indicated a 10c. tailing on a $6 head. In 1918 a 300-ton flotation mill using Minerals Separation machines was built based on the results obtained. However, when the mill began full-scale operation, mill heads did not come up to expectation, being only $4; also the-tonnage was considerably less than had been expected. Flotation mill tailing assayed 15c., indicating a recovery of over 96 per cent, so that excellent metallurgical results were obtained. The operation was a success but the patient died.

Jan 1, 1932

By G. B. Sazuyer

DEVELOPMENTS respecting beryllium during the past year have been sufficient to center attention on it as likely to be the most important of any of the chemical elements that have recently found a place for themselves in technical industry. This importance is only potential, however, largely because adequate supplies of beryllium ore will be necessary. The beryllium industry will be only as great as the mines which support it. To find and develop large mines will be the problem. Chief of the immediate commercial developments in the United States is beryllium-copper and its espousal by Anaconda and Riverside even at present high prices. According to the pamphlets of these companies, it ap¬pears that beryllium is to copper nearly what carbon is to iron. When one considers that the tensile strength of pure copper is about 33,000 lb. per sq. in., but that the addition of 1.5 to 2.5 per cent of beryllium produces a heat-treatable alloy with a maximum tensile strength of 220,000 lb. or over, the analogy to carbon and iron is made strikingly, clear. Striking among the properties of beryllium-copper is its resistance to fatigue, claimed to be equal or superior to that of spring steel. It needs little imagination to foresee a great industry for this alloy alone.

Jan 1, 1934

By George W. Pawel

OWING largely to its value as a toughener and strengthener of steel for both industrial and military purposes, nickel is playing, an important role in the current war. It is fine of the metals in which the Allies enjoy a definite edge over the Axis nations and this time there is no place to which the Germans may send another submarine "Deutsehland" and expect to pick up a cargo of nickel to replenish their exhausted supplies. Total world nickel production thanks almost entirely to the expanded operation of the International Nickel Co. of Canada at Sudbury must now be at the rate of around 175,000 tons a year scarcely more than 5 per cent of which is accounted for by Germany, Italy and Japan. This represents more than four times the world output at the end of the first World War.

Jan 1, 1943

THE decision of the lower court (United States District Court for the Southern District of New York) in the suit of the Dwight & Lloyd Sintering Co., vs. John E. Greenawalt has been affirmed by the United States Circuit Court of Appeals for the Second Circuit. In the original suit, infringement of seven patents was alleged, these covering the process of producing a sinter .out of finely pulverized metalliferous ores as practised in shallow pans operating intermittently in distinction to the Dwight 6: Lloyd continuous machine. The court found that the long delay in bringing suit precluded any recovery of profits from the defendant under the basic down-draft sintering patent, although Dwight & Lloyd are recognized as the inventors of this' contribution to the art and its .importance is acknowledged.

Jan 1, 1928

By Boris J. Kochanowsky, Burke O. Trafton

Because of the strict requirements on the quality of limestone that are dictated by the users, the operator was compelled to find new approaches to produce a product of uniform and acceptable quality. The raw material is controlled and monitored every two minutes by a special computer in order to ensure its quality. The required minimum and maximum quality constraint had an adverse effect on performance and consequently cost. In order to improve this performance, a Monte Carlo simulation model was developed and tested for the optimal truck allocation. The input data is based upon the distribution of equipment performances and costs.

Jan 1, 1969

By R. S. Bradley

WHAT are known as insulating firebrick are lightweight firebrick with low thermal conductivity designed primarily for use in direct contact with furnace gases. These are a recent development in the refractories industry, and are really an outgrowth of the type of insulating brick suitable for use behind refractory walls developed by the insulation manufacturers. To differentiate between these two types of brick, the manufacturers have recently agreed upon the use of the term "Insulating Firebrick" to apply to the type of brick suited for use in direct contact with furnace gases, and the term "Insulating Brick" for the type suitable for use behind refractory walls. Insulation was applied to steam pipes as far back as 1900. This was a low-temperature insulation, the most common type being magnesia blocks. The next development was applying insulation to the outside of furnace walls, a service which necessitated an insulating material of higher temperature resistance. Natural diatomaceous earth, both in the powdered and brick form, was used; this was efficient and is still used extensively for backing up refractory walls where the inner surface temperature of the insulation does not exceed 1600° F.

Jan 1, 1937

By ANDREW McVILLIAM, WILLIAM H. HATFIELD

AT the 1902 May meeting of the Iron and Steel Institute, the, authors presented a paper on " The Elimination of Silicon in The Acid Open-Hearth," wherein they recorded a few typical examples of certain Siemens charges out of a very large number specially watched for the purposes of that research. The main deductions drawn from those experiments have been accepted in all the intelligent criticism during or after the discussion on the paper. One opinion, however, was rigidly held by all who mentioned the matter, with the single exception, perhaps, of Mr. Lange, and that was the necessity for the attainment and the maintenance of an abnormally high temperature in order that the percentage of silicon in the metallic bath might increase, or that an unusually large proportion of silicon might be retained in the metal. The original decision was ar-rived at on the results of scores of trials, and has since been the subject of frequent experiment. The authors still retain their opinion that although, naturally, a higher temperature will accelerate the (probable) action between the carbon of the steel and the excess silica of the slag, they then fairly proved, and have now abundantly confirmed the fact, that around the temperatures occurring in Siemens steel-making practice the chemical composition of the slag, particularly with regard to its acidity, is the factor which determines whether the percentage of silicon in the molten steel shall increase or decrease. In the discussion in 1902 Mr. Saniter called attention to Mr. H. H. Campbell's work, and in the reply the authors also mentioned that of Messrs. Winder and Brunton of 1892, the two

Mar 1, 1905

By Philip D. Wilson

FEAST and famine-or, chronologically, famine and feast-have characterized the aluminum supply program during 1943. Fortunately for the war effort the famine phase is over and aluminum production is now in the happy position of being abundantly able to supply all the requirements of the armed services plus a monthly surplus which is building up a substantial stock pile as a reserve against any contingencies. But the present condition of oversupply cannot be attributed to the super-efficiency of the aluminum production program which was designed to take care of the over-all requirements of the war with little or no margin of safety. The present more than comfortable situation is due primarily to the fact that the armed services generally have not consumed anything approaching the amount of aluminum which their requirement estimates indicated.

Jan 1, 1944

By FREDERICK C. BROWN

THE practice of fine-grinding is now being so successfully - carried on in some fields, notably in West Australia, and its advisability has been so frequently pointed out' that the matter in this paper is not put forward as being new ; its chief object being to call attention to the importance of fine-grinding in the treatment of comparatively low-grade ores. I have been engaged during the last five years in the cyanide-treatment of ores in the Ohinemuri district (North Island), New Zealand, and I consider that, in the near future, extremely fine-grinding (almost sliming) will become a very important feature of the milling-methods in this field, since it seems absolutely necessary to reduce the most of ores to a very fine state of division if a high extraction is to be obtained; and, in most cases, the extra percentage of saving will leave a good margin above the increased cost of treatment due both to the fine-grinding and to the interest on the capital spent for the grinding-machinery. The average ore of the Ohinemuri field is composed of a quartz-gangue with some calcite, carrying the gold-value in the form of an alloy of gold and silver in about equal proportions, and the silver-value in the form of mixed sulphides of silver, usually associated with a considerable amount of iron pyrites. In the upper levels, the ores are decomposed and carry large quantities of black manganese oxide and some iron oxide, but, as. depth is reached, the decomposed ore gives place to sulphides and, in some mines, rhodonite, manganese silicate, is present in fairly large quantities. The average value of the

Jan 1, 1906

By Luis Toron, Salvador Cortes-Obregon

John D. Price (Colorado Fuel and Iron Corp., Pueblo, Colo)—The paper on the coal fields of the Oaxaca district as prepared by engineers Toron and Cortes-Obregon of the staff of the Bank of Mexico bears witness to the thorough and careful way in which the men associated with this organization perform their work. There is little to be added to their paper in way of discussion other than to confirm and amplify some of their statements. Since the only extensive and well-developed field of coking coal lies in the northeastern section of the country adjacent to Sabinas in the state of Coahuila, it follows that blast furnace plants would be located in that same region. Two such plants are now operating at Monterrey and Monclova, using coke produced at the Sabinas district mines. But the nearer of these two plants is 600 miles from Mexico City and even farther from the center of population. Transportation of products from these mills to the market area is therefore expensive, both because of the distance and the difficulty of the terrain over which it must be carried. The development of an integrated steel industry closer to the center of population has therefore long been a goal toward which the Mexican technicians have been striving. While the presence of coal of some grade has been reported in many of the states, and many ideas have been advanced regarding its possible uses in iron and steel production, deposits of anthracite in Sonora and the various coals of the Oaxaca district as reported on in this paper are the only ones that have been explored in a serious manner. The coking coal from the Mix-tepec zone appears to offer promise of producing a coke which could be used in a standard blast furnace. Several problems are indicated, however: 1—The ash in the coal is high as mined, but indications are that it can be washed to an ash content of 15 pct with a recovery of 70 pct of washed coal. 2—Such washing would increase the volatile content from 17.4 pct to about 20 pct, and in a byproduct oven this should give a coke yield of close to 80 pct with an ash content of coke under 20 pct. 3—A free swelling index of 5 appears low for a good coking coal, and below that of the coals from the Sabinas district, which show between 6 and 9. But washing of the coal should result in an improvement in this regard; in the United States coals from Utah with an index even lower than 5 have made a usable coke. 4—A coal with volatile as low as 17.4 in raw coal and 20 in washed coal would come close to being classed as a low-volatile rather than medium-volatile coal, and low-volatile coals are notorious for their high expansion properties. Several plants in the United States are making coke from straight medium-volatile coal of 26 to 28 volatile content, and one at Rosita,, Mexico, from coal of 25 volatile. But no plants to my knowledge are using coal as low as 20 volatile. Since the Rosita coal appears to be a borderline coal from the angle of its expansion properties the coking of one of the straight lower volatile must be approached with caution. 5—There are few coals possessing any degree of coking properties which cannot be used in coke production by careful attention to its preparation and blending. The fact that coals of other types are available in this same region make improvement through blending very possible. 6—There are other workable methods of reducing iron ore other than the conventional coke-blast-furnace method. These will not be discussed here but it is known that their use has been considered. The technicians of not only Mexico but also of the other Latin American countries are keenly aware of their natural resources and their national needs. This paper emphasizes the fact that the Mexican technicians are working on their problem and attempting to speed the day of self-sufficiency for their country. Salvatore Cortes-Obregon (author's reply)—I wish to thank Mr. Price for his kind remarks. The Mixtepec coal as shown in Table II has 30 pct ash and a free swelling index of 5, but when the same coal is washed to 15 pct ash it has a free swelling index of 8 to 9 and the volatiles increased from 17.4 to 20.7 pct. A satisfactory coke has been produced from blends made in the Mexican laboratory using at least 40 pct of the Mixtepec coking coals with the other Oaxaca non-coking coals. Koppers in Germany report good coke obtained from the Oaxaca coal with a blend of 80 pct Mixtepec coal. Consideration is being given the possibility of using methods other than the conventional blast furnace for the reduction of iron ore near the Oaxaca area; electric furnaces appear promising. The non-coking coals could be used to produce cheap electric energy and the coking coals to make metallurgical coke.

Jan 1, 1955

By C. W. Chen

MARTENSITE transformations in ß Cu-Al alloys have been studied by Greninger1 and other investigators. According to Greninger, the parent phase ß1 an ordered body-centered-cubic structure obtained from ß phase by suppressing the eutectoid decomposition, transforms into an ordered hexagonal-close-packed phase in composition containing 12.9 to 14.7 pct Al. The M, temperature decreases with increasing aluminum content; for the alloy containing 14.5 pct Al, for example, the ß1??' transformation occurs below room temperature. More recently, Kurjumow2 studied the transformation in ß Cu-Al alloys with the addition of nickel. His report stimulated new interest in the subject due to the observation of completely reversible transformation without hysteresis in the transformation temperature ranging from 10° to —10°C. In the present paper some characteristics are described of the transformation of Cu-Al-Ni alloys that were partly studied by Kurjumow. Experimental Procedure High purity copper (99.999 pct) and aluminum (99.99 pct) and electrolytic nickel were used in the preparation, by the Bridgman technique, of single crystal specimens which contained aluminum and nickel of 14.5 and 0.5 to 3.0 pct, respectively. Polished surfaces were prepared mechanically. Specimens were then chemically etched to remove distorted material, homogenized at 1000°C for several hours, and quenched drastically to room temperature in a 10 pct NaOH bath to produce the parent phase ß1. The transformation was studied under a microscope and, in some cases, recorded by means of motion pictures. A device similar to that designed by Greninger and Mooradian3 was used to cool and reheat the specimens. Results and Discussion When the specimens were cooled below room temperature, the ß1 to ?' transformation began at 10°C with the appearance of ?' crystals In relief, Fig. la. As the specimen temperature dropped further, the transformation continued, either by the growth of the ?' crystals, with the ß1 — ?' interface moving into the ß1 phase, Fig. 1c and 1d, or by the formation of new ?' crystals, Fig. 1b. As a consequence of the former process, banded structure is observed as a common feature of the low temperature phase. According to the theory of the formation of martensite by Wechsler, Lieberman, and Read,' the bands of ?' phase are probably twin-related, as is the case in the diffusionless phase change of In-T1 alloys,5 but this was not revealed by X-ray tech- niques. New ?' crystals, in needle form, often emerged suddenly across the ?' bands during the transformation. These acicular crystals then grew, both in length and in width, see Fig. 2a through 2d. The transformation on cooling is completed at about -35°C. Upon heating, the reverse transformation started at —10° C, in a manner nearly opposite to the transformation on cooling, and completed at 35°C. There was no noticeable change in the transformation temperature when the nickel content was varied within the limits previously mentioned. Through control of the specimen temperature, the transformation can be started, stopped, or reversed at will. This phenomenon has frequently been observed in the martensite transformation of many nonferrous alloy systems. Other systems are Au-Cd6 and In-Tl.5 ow-- ever, in the latter systems, the transformation is accomplished by single interface motion if the specimen composition is homogeneous and the temperature gradient in the specimen is uniform and sharp, whereas in the Cu-Al-Ni specimens, only multiple interface transformation is observed. The speed of the interface motion appears to be a functionof the rate of temperature change and the temperature gradient across the specimen length. In one case, in which the temperature increased at the rate of 10°C per min and there was no temperature gradient along the specimen axis, the speed of the disappearance of a ?' plate was determined, by the study of the motion pictures made, to be 26 µ per sec. Quench markings were observed on the polished surfaces of specimens. The markings were grouped into one or more sets of different orientations, and were parallel in each set. The ?' plates formed in subsequent transformation were parallel to the markings, indicating that the ?' plates and the quench markings had the same geometric relation-ship to the ß1 matrix. The quench markings on two intersecting surfaces of a specimen were therefore used in the determination of the habit plane of transformation, by the trace method suggested by Barrett.' Results obtained from five sets of markings in three specimens indicate that the habit plane is an irrational plane about 2" from one of the {221} planes. This is very close to the habit plane (3" from 221 planes) of ß Cu-Al alloys containing more than 13.0 pct Al.1 The martensite transformation of Cu-Al-Ni alloys is reproducible. No sluggishness was found between consecutive transformation cycles, although a slight difference in the distribution pattern of the ?' plates was observed, compare Figs. Id and 2d. The transformation can be strain-induced. This characteristic has been tested by a simple method. When a specimen was elastically strained slowly in a vise, ?' plates were gradually produced in the same fashion as during transformation on cooling, This test was done at room temperature, and thus above the M,

Jan 1, 1958

By K. A. Gschneidner, O. D. McMasters, T. J. O’Keefe

X-ray diffraction, differential thermal, ad rnetallo-graphic methods were used to establish the Dy-Pb Phase diagram. Lead additions lower the 1377°C transformation temperature of dysprosium to 1360°C leading to an inverted peritectic reaction. The 327°C melting point of lead is lowered by dysprosium additions to about 326°C yielding a eutectic reaction. A second eutectic reaction occurs at 13.3 at. pct Pb and 1200°C. The dysprosium-richest intermetallic compound DysPb3 melts congruently at 1695°C and crystallizes in the hexagonal Mn5Si3 (D8,) type structure. The peritectic decomposition temperatures for the remaining compounds are Dy5Pb, at 1555C, DyPb2 at 955C, and DyPb3 at 880°C. A fifth compound near the DyPb stoichiometry exists over a 310°C temperature range decomposing at 1130°C by means of an inverted peritectic reaction and melting incongruently at 1440°C. The crystal structures of the compounds are discussed. A systematic study of the rare earth-lead alloy systems is underway in an effort to supply information concerning the alloying behavior of the rare earth metals. The Dy-Pb phase diagram is the fourth system to be investigated in this study. The Yb-Pb,1 Y-Pb,2 and Eu-Pb 3 diagrams have been published recently. Utilization of the rare earth series of metals as a research tool in this manner should yield a better understanding of alloy formation. EXPERIMENTAL PROCEDURE Materials. The lead used in this investigation was obtained from Cominco Products, Inc., and was specified to be 99.99 pct pure. The dysprosium was prepared in this Laboratory by the calcium reduction of the fluoride followed by distillation of the dysprosium. The major impurities in the dysprosium in ppm are: A1 (<40), Ca (400), Er (<50), Gd (<200), Ho (<200), Mg (<50), Si (30), Ta (400), Tb (<100), Y (<50), 0 (651, H (15), N (not detected), F (430), C (35). Alloy Preparation. Most of the alloys were prepared by melting weighed amounts of dysprosium and lead in sealed tantalum crucibles. The tantalum crucibles were sealed by are-welding in a He-Ar atmosphere welding chamber. Thus the alloys are in contact with He-Ar at about 1 atm pressure. Homogenization was achieved by holding them in the liquid state for about 1 hr, cooling, inverting the crucibles, remelting, and repeating the process at least twice. Since these alloys were prepared in sealed tantalum crucibles, chemical analysis for final composition was thought to be unnecessary. No detectable reaction of these alloys with the tantalum crucible was observed by metallographic examination. Metallographic evidence was also used to confirm the homogeneity of some of the alloys prepared in this manner. The compositions of a few alloys, which were prepared by nonconsum-able are-melting, were corrected for the small weight losses involved by assuming that the weight loss is due to vaporization of lead. The specimens obtained from the alloy samples were prepared under a dry-argon atmosphere because they were rapidly attacked by air and moisture. Thermal Analysis. Differential thermal analysis methods were used to determine the liquidus curves and reaction horizontals of the system. Both Pt vs Pt + 13 pct Rh and W + 5 pct Re vs W + 26 pct Re thermocouples were used to measure the temperature. An X- Y recorder was used to record the specimen temperature and differential electromotive force between the specimen and molybdenum standard. The arrest temperatures were measured potentiometri-cally. The accuracy limits (* values) associated with the reaction temperatures obtained by this method were estimated on the basis of both the reproducibility of the particular temperature value and the accuracy of the thermocouple at a given temperature. Liquidus temperatures were obtained from cooling arrest data while both heating and cooling arrest data were used to establish the horizontals of the diagram. Heat treatments during the thermal analyses of the alloys between 40 and 70 at. pct Pb were necessary in order to approach equilibrium conditions. The samples were held at temperatures between the various peritectic horizontals for l to 2 hr before the thermal analyses were continued. The entire range of compositions was investigated at the expense of a minimum amount of materials by adding appropriate amounts of lead to master alloys. More than sixty alloys were analyzed by this differential thermal method and for each alloy the results given herein are taken from two or three heating and cooling cycles. X-Ray and Metallographic Methods. Slice specimens for metallography and powder specimens for X-ray diffraction were prepared from rod-shaped samples which had been melted in sealed 0.62 5-cm-diam tantalum crucibles. The specimens were heat-treated in sealed tantalum crucibles which were protected by sealing them in argon-filled quartz ampules. Quenching was accomplished by breaking the ampules in ice water after heat treatment. X-ray powder specimens were sealed in 0.3-mm-diam glass capillaries under a dry-argon atmosphere. Copper, iron, and chromium radiation were used to obtain the powder patterns for these alloys. More than 150 powder patterns were obtained for specimens of various compositions and heat treatments. Included in these were several patterns for specimens which had purposely been oxidized. Patterns from specimens which had been accidentally exposed

Jan 1, 1969

By Amitava Gangulee, Michael B. Bever

The effects of changes in short-range order on some thermodynamic, electrical, and mechanical properties of the silver-rich Ag-Mg solid solutions have been investigated. The heats of formation at 273°K of several alloys after two different thermal treatments were measured by liquid metal solution calorimetry. Their electrical resistivities were measured at temperatures ranging from 4° to 773°k. Tensile tests and microhard-ness measurements were carried out at room temperature. An effective short-range order parameter and an effective interaction energy are defined. The measured changes in the properties are interpreted in terms of these quantities. The short-range order parameter is evaluated separately from calorimetric and X-ray data; the results are in fair agreement. Increasing short-range order lowers the resistivity of- the silver-rich Ag-Mg alloys but does not measurably affect the temperature dependence of the resistivity. Short-range order increases the yield stress of these alloys but does not affect the ultimate tensile stress. Changes in the effective short-range order parameter independently obtained from measured changes in the heat of formation, resistivity, and yield stress are in fair agreement. THE thermodynamic, electrical, and mechanical properties of solid solutions have been investigated as functions of composition in many alloy systems, but the effects of configurational variables, such as short-range or long-range order, on these properties have received much less attention. The silver-rich terminal solid solutions in the system Ag-Mg are well-suited for the investigation of the effects of order. The composition of these solid solutions may be varied over a range extending to about 27 at. pct Mg.1 Appreciable short-range ordering is likely to take place in these solid solutions; the degree of short-range order can be varied by suitable thermal treatments. In the alloy Ag3Mg long-range ordering is possible.2 This paper is primarily concerned with the effects of short-range order on some thermodynamic, electrical, and mechanical properties of the silver-rich Ag-Mg solid solutions.-The long-range ordering transition is the subject of a concurrent paper.3 1) EXPERIMENTAL PROCEDURES 1.1) Preparation of Specimens. Ag-Mg alloys containing up to 26.4 at. pct Mg were prepared by melting 99.99 pct pure Ag (obtained from Baker Chemical Co.) and 99.99 pct pure Mg (obtained from Eastman Chemi- cal Co. or Johnson Mathey & Co.) in graphite crucibles under molten potassium chloride. The solidified ingots were homogenized at 823°K for 10 days in evacuated Vycor capsules. A surface layer 6 in. thick was then removed by machining. The ingots were swaged into rods (2.5 mm diam) which were drawn into wires (1.0 mm diam). The wire specimens were annealed at 773°K for 24 hr in vacuum and either quenched into iced brine or cooled to room temperature over a period of 15 days. The average grain diameter (obtained from the linear intercepts) was about 0.1 mm. 1.2) Calorimetry. The heats of formation of the alloys were measured in a tin solution calorimeter as the difference in the heat effects of alternate additions of samples of an alloy and the mechanical mixture of its component elements. The additions were made from 273°K to the bath at about 623°K. The heat effect on addition of the alloys was approximately 5.5 kcal per g-atom. The procedure and the method of calculation have been described.4 1.3) X-Ray Diffraction. Short-range order parameters of two alloys were calculated from diffuse scattering intensities,&apos; obtained with briquettes made from powdered specimens. A GE-XRD 5 diffractometer with filtered copper radiation was used. The absolute intensities were based on calibrations with paraffin. 1.4) Resistivity Measurements. The electrical resistivities were measured by a potentiometric method in which the potential drop across the specimen was compared with that across a standard resistance. For measurements below room temperature, the specimens were immersed in liquid helium (4°K), liquid nitrogen (78°K), dry ice and trichloroethylene (195°K), or ice and water (273°K). Measurements above room temperature were made on specimens held in a furnace under helium or in vacuum. The resistivity measurements were reproducible to ±0.5 pct or less. 1.5) Mechanical Tests. Tensile tests were carried out at room temperature with a Tinius-Olsen XY elec-tromatic Universal testing machine. Wire specimens (nominal gage length 1 in.) were used. The strain was measured with an extensometer, which had a sensitivity of 4 x 10-5; the strain rate was 10-3 min-1. Microhard-ness measurements were made with a square-pyramid indenter and a 100-g load.11 2) RESULTS AND DISCUSSION All measurements were made on two parallel sets of specimens, one quenched and the other slowly cooled from 773°K. The reported values are the averages of at least three measurements. In the range of magnesium concentration substantially below that of the composition Ag3Mg, quenched alloys have less short-range order than slowly cooled alloys. As the magnesium concentration approaches that of Ag3Mg, slow cooling develops long-range order. Quenching sup-

Jan 1, 1969

By Shiou-Chuan Sun

THE fact that coals of different ranks and even of the same rank differ greatly in their amenability to iroth flotation is well known. In recognition of the need for an explanation of this phenomenon, two hypotheses have been suggested. Wilkinsl reported that the floatability of coals increased with an increase of the carbon content or rank. This postulate is handicapped by the fact that bituminous coals that possess moderate carbon contents are actually more floatable than anthracite coals that have high carbon contents, as shown in columns 6 and 9 of Table I. Taggart and his associates&apos; implied that the difference of floatability between bituminous and anthracite coal was caused by the variation of carbon-hydrogen ratio. This is not applicable to the relative floatability of other coals and carbons. For example, column 11 of Table I shows that the carbon-hydrogen ratios of low-floating lignitic coal and non-floating animal charcoal are not only smaller than the moderate-floating anthracite coal, but are also similar to the high-floating bituminous coal. Furthermore, according to this hypothesis, high temperature coke-A (464), Ceylon graphite (1238), and lamp-black (357), all possessing extremely high carbon-hydrogen ratios, should be less floatable than other substances having much lower carbon-hydrogen ratios such as high volatile-B bituminous coal (11.9 to 22), anthracite coal (35.7 to 60.5), lignitic coal (15.6 to 33.6), and charcoal (13 to 26.2). However the former group is actually more floatable than the latter group. In this paper, a surface components hypothesis is Proposed to explain the different floatabilities of coals, carbons, and hydrocarbon minerals. The validity of the hypothesis is experimentally supported by the actual floatability, natural floatability, wettability, and adsorbability for neutral oils of coals, carbons, and hydrocarbon minerals tested. The combustible recovery of the flotation results, as used in this paper. was calculated from Eq. 1: P (100-Ep) 100 RWCP Rc= [1] F (100-E,) C, where R, is the percent combustible recovery; F and P are, respectively, the weight of feed and the weight of concentrate or product; E, and Ep are, respectively, the total percent of ash plus moisture in feed and in concentrate; Ru. is the percent weight recovery: and C, and C, are, respectively, the percent of combustible in feed and in concentrate. Except for ash and moisture content, all chemical components of a coal are assumed combustible. The experimental work included studies on flotation, ultimate and proximate analyses, contact angle tests, extractions of bitumen-A with benzene, adsorptions for liquid hydrocarbons, and wetting tests. Most of the flotation experiments were performed in a laboratory Fagergren machine; others were tested in a small Denver machine. The solid feed for the former was 300 g and for the latter was 30 g. The solid materials used for flotation were crushed to —48 mesh. After the mineral pulp in the flotation cell was agitated for 6 min and the pH was adjusted to 7.5 & 0.2 with sodium hydroxide or hydrochloric acid, a petroleum light oil having a viscosity of 5.73 centipoises at 77 °F was added and conditioned for 2 min. Finally, pine oil was introduced and the froth was collected for exactly 3 min. The weight ratio of petroleum light oil to pine oil was kept constant at 1.5 to 1. Tap water was used for all flotation tests. Contact angles were measured with a captive bubble machine. For each coal sample, three specimens were mounted in transoptic mounts and polished with levigated alumina, first on a sheet glass, then on a cloth-covered metal polishing wheel. The polished specimen was first washed with distilled water and wiped thoroughly on a cleaned linen pad, then transferred into the pyrex cell of the captive bubble machine and conditioned for 6 min., and finally measured for contact angles at three or more points. Except where otherwise stated, the induction time for each measurement was 1 min. The contact angle representing each material was obtained by averaging the measurements of three specimens. The linen pad was first washed with warm distilled water, then boiled 30 min in a 2N sodium hydroxide solution, and finally washed with distilled water until no trace of sodium hydroxide could be detected in the decanted solution. The cleaned linen pad was stored under distilled water. Immediately before using, the pad was rewashed and transferred into a clean pyrex petri dish partly filled with distilled water. The glassware and rubber gloves used were cleaned by soaking in sulphuric acid-potassium dichromate cleaning solution, followed by rinsing with distilled water. The polished specimens were handled only by glass forceps. The ultimate and proximate analyses were made in accordance with the ASTM standard procedures for coal and coke. The extractable bitumen-A was determined by weighing 1 g of —100 mesh sample and placing it in a desiccated and weighed ASTM aluminum-extraction thimble. The thimble was placed in condenser hooks and inserted into an extraction flask containing 100 cu cm of benzene. The flask was heated and the benzene vapor was condensed by water coils. At the end of 24 hr of percolation, the thimble was removed, desiccated, and weighed. Loss in weight of sample was taken as bitumen-A and calculated to dry and ash-free basis.

Jan 1, 1955

By I. J. Hegyi, J. J. Tietjen, H. Nelson, J. I. Pankove

The fabrication of p-n junctions in GaAsl-,P, alloys by a vapor-phase gowth technique has for the first tirne resulted in room-temperature injection lasers capable of operating over a broad range of wavelengths extending into the visible region of the spectrum. The shortest wavelength achieved to date is 6750A at room tetnperature. In addition, at 78°K the threshold current density values for these lasers are generally the lo~vest reported, and the emitted radiation extends to the lozc,est wavelength ever attained (6350A). With lasers fabricated from material containing 14 pct Gap, quanticm efficiencies of 26 pct and peak power outputs of 25 zu were obtained at room temperature. ALTHOUGH room-temperature operation of GaAs injection lasers has been well-documented,&apos;-5 the operation of GaAsl-,P, (x > 0) laser diodes has been restricted to relatively low temperatures.8-&apos;0 This has been previously attributed5, 7, 10-12 partially to the difficulty of preparing single-crystalline GaAsl-& alloys having a high degree of chemical homogeneity and purity. Also, with these materials it has been difficult to prepare high-quality, abrupt p-12 junctions by diffusion techniques; and, in turn, this has made it difficult to obtain optimum electrical properties for room-temperature operationL3 in the resulting laser diodes. As a result, GaAsl-,P, laser diodes have not been efficient enough to permit operation at room temperature. For example, using diffused structures, only a few diodes were obtained which could be operated even close to room temperature (255K)." Recently, a vapor-phase growth method of preparing epitaxial deposits of GaAsl - .P, alloys has been described,14 and the high-purity and homogeneity of these materials has been previously demonstrated. Of special significance, with this technique, n- or p -type doping can be initiated or discontinued at any time and at almost any rate during the crystal growth so that the donor and the acceptor concentrations can be easily controlled to obtain desired impurity profiles. This permits high-quality, abrupt p-TZ junctions to be vapor-phase grown entirely during the crystal growth process, so that diffusion or other p-n junction fabrication processes are unnecessary. After growth, the device does not have to be heated to elevated temperatures, which avoids the possible unwanted introduction and motion of both impurities and lattice defects. Using the vapor-phase growth method cited above, over 300 room-temperature injection lasers have been prepared from GaAsl-,P, alloys having compositions in the range of 0 5 x 5 0.41. These lasers have emitted cohe~ent radiation in the spectral range of 8350 to 6350A at 78°K or from 9000 to 6750A at room temperature. The threshold current densities of the best lasers are independent of the alloy composition over the range 0 < x < 0.2 and compare favorably with values for good GaAs lasers.&apos; MATERIAL PREPARATION Multilayer, epitaxial deposits of GaAsl-,P, alloys are prepared by a vapor-growth technique described elsewhere.14 With this technique, the individual layers which comprise the multilayer structure are prepared sequentially in the deposition apparatus without interrupting the crystal growth. The epitaxial layers are deposited on GaAs substrate surfaces oriented normal to the ( 100) direction. The substrate wafers employed in this study were usually doped with tellurium to an electron concentration of approximately 2 x 10" per cu cm. To avoid strains, the first 10 to 15 p of the deposited material is uniformly graded from pure GaAs to the specific GaAsl- ,P, alloy composition of interest. The GaAsl - ,P, alloy growth is then continued to form a layer of constant composition having a thickness in the range of 25 to 75 p. Both the graded region and the layer of constant composition are doped with selenium to an electron concentration of about 2 x 10" per cu cm. The p region of the diode is then incorporated in the crystal by abruptly changing the dopant concentrations in the vapor phase to facilitate doping with zinc. This layer has a hole concentration of approximately 3 X 1019 per cu cm and typically is 50 p thick. DEVICE FABRICATION In general, the GaAs substrate and the region of graded composition are removed. Ohmic contacts are made to the n-type side by tin evaporation and to the p-type side by an electrodeless nickel deposition. This is followed by an electrodeless deposition of gold on both sides. The crystal wafer is then cleaved along (110) planes and sawed into rectangular parallelepipeds. Typical dimensions are 100 by 300 for the junction area and 100 µ for the diode height. The diodes are either soldered to a copper stud or pressure-mounted in a copper clip. RESULTS AND DISCUSSION Approximately 400 laser diodes having compositions in the range of 0.41 have been prepared by the method described above. Each laser was routinely tested at liquid-nitrogen temperature. The lasers were operated with l-psec current pulses at a repetition rate of 60 pulses per sec. The parameters of greatest practical interest are the photon energy or wavelength of the laser output and the threshold current density. Fig. 1 shows the variation of photon energy with alloy composition at 78°K. The composition was determined from the lattice constant of the material obtained by X-ray back-reflection measurements. Although there

Jan 1, 1968

COLLECTIVE bargaining, hereto-fore loudly proclaimed as one of the stout timbers of the Republic, has passed from the picture. The coup de gr[a]ce was struck by the President of the United States when he ignored his vested legal prerogative and seized the steel industry by the dubious authority of, his "inherent powers." Autocratic judgment by a single official replaced arbitration by the steel industry and labor union. This is the outcome of a battle which has been bitterly waged for months in the hazy atmosphere created by well oiled propaganda machines. Prior to government intervention, there was no clear picture of the issues at stake. All parties concerned marshalled their accountants to conjure up figures proving their respective contentions. The results were fed into public relations departments for embellishment and dissemination. Thus, the public was asked to believe on one hand, that the steel worker, who is second only to the coal miner in hourly wages, was entitled to an increase in pay and other benefits. Nothing was said about the effect-of such an increase on the national economy. Industry in turn pointed to declining profits after taxes, but failed to mention the more than a billion dollars spent on plant expansion, in addition to the payment of substantial dividends for 1951. With the intervention of the administration, the immediate issue became clear to freedom-loving Americans. Is the executive branch of the government above the law, or is it supposed to uphold and carry out the .laws of Congress? The present administration forgot that it is a servant of the public and has become despotic. The American people must obliterate this dangerous precedent which has been set by the administration or accept the. ominous consequences of submission. Fortunately, the strongest weapon of the citizen-the ballot -still remains. When democratic procedure is restored, stabilization of the economy will continue to challenge us. This is the main public stake in the steel controversy. Only a solution based on bed-rock democracy will work. If the emergency is real, and we must assume that it is, this is the time for sacrifice. Industry and labor must meet without rancor to resolve wage contracts through collective bargaining. The government role, under emergency conditions, must be to objectively maintain wage, and price ceilings in the interest of stabilization. Political expediency cannot be permitted to&apos; influence these controls. Politics and not the public weal have been the guide lines for too long. We are at the cross roads. By all sober judgment, this is the time for Americans to take a militant interest in their government today. Tomorrow will be too late.

Jan 1, 1952