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By D. H. Forbes, I. B. Cadoff, H. M. Manasevit

Single-crystal silicon films have been obtained on several natural crystal faces of BeO using the thermal decomposition of silane and the hydrogen reduction of silicon tetrachloride. From an analysis of X-ray diffraction data it was determined that the following film-substrate orientation relationships exist: (111) Si 11(0001) BeO, (111) Si 11(1011) BeO, (100) Si 11f1010) BeO. and (110) Si 11(1010) BeO. An analysis of the crystallographic relationships between the film and substrate indicates that a match occurs between the silicon atoms in the film and the berylliuni ion sites in the substrate. This correspondence is in agreement with previous work on the deposition of silicon on sapphire.1-3 silicon on spinel: and tungsten on sapphire. The high resistivity, thermal conductivity, and radiation resistance of beryllium oxide make it an important substrate material for the deposition of thin films of silicon or other semiconductors. The importance of semiconductor-insulator composites to the field of integrated microelectronics has been well-documented in the case of silicon on sapphire.'-' The successful growth of large-area single-crystal silicon on an insulator, sapphire, was first reported in 1963.1,2 Since that time studies have been made of the crystallographic relationships between the deposited film and the sapphire substrate. On the basis of the observed relationships, a model has been proposed relative to the crystallographic requirements for epitaxy between the semiconductor film and the metal oxide substrate.3 It is proposed in this model that epitaxy is the result of a match between atoms of the deposited film and the metal ion sites of the substrate plane. This match is not limited to a 1 to 1 correspondence between sites in the two lattices. Sub- sequent studies of the deposition of silicon on spinel4 and tungsten on sapphire5 have yielded data which support this model. On the basis of this previous work it was felt that silicon on BeO should also fit this model. In the present study, the choice of substrate orientation was limited to the natural faces of synthetic BeO crystals. Of the faces available, the (0001) plane seemed the most favorable for epitaxial growth. EXPERIMENTAL PROCEDURE Silicon films were deposited from silane and silicon tetrachloride in the apparatus shown in Fig. 1. The hydrogen ambient gas was purified by passage either through a DEOXO unit, molecular sieves, and a liquid nitrogen cold trap, or through a heated Pd-Ag thimble. The gas was then mixed with the silicon source materiai and passed over the substrate which lies on a spacer above an inductively heated silicon pedestal. The following deposition conditions were used: a hydrogen flow rate of 3 liters per min with silane and silicon tetrachloride concentrations of 0.2 mole pct and a pedestal temperature of 1175" * 5°C as observed with an optical pyrometer assuming an emissivity of 1.0. Deposition was preceded by a 15- to 30-min hydrogen-etch period conducted at a temperature of 1275°C (obs). Adherent silicon films from 2 to 10 u were grown on the various BeO faces. The substrates were synthetically grown beryllium oxide single crystals ranging from 5 to 10 mm in

Jan 1, 1967

By Frederick N. Rhines, William A. Anderson

The investigations of Wymanl have demonstrated that copper deoxidized with several of the commonly used agents that confer immunily to ordinary hydrogen em-brittlement can still be embrittled if it is annealed alternately under oxidizing and reducing conditions. During the oxidizing cycle, oxygen diffuses into the copper and frequently deposits a subscale composed of the oxide of the residual deoxidizing agent. Upon subsequent reduction with hot hydrogen, the copper becomes ruptured along the grain boundaries to a depth sharply limited by the previous penetration of oxygen as delineated by the inner boundary of the subscale. Obviously the sensitivity to this kind of hydrogen embrittlement is engendered by the introduction of oxygen during the oxidizing anneal, but beyond this the mechanism of the process, and hence the controlling factors, remain obscure. There are several possibilities: (I) oxygen dissolved in the copper matrix of the subscale may, upon cooling prior to the hydrogen anneal, precipitate as cuprous oxide which is subsequently reduced by hydrogen as in the familiar case of hydrogen embrittlement; (2) oxygen in solid solution in copper may itself confer susceptibility to embrittlement by hydrogen; (3) the normally refractory oxides such as those of aluminum, silicon and titanium may themselves be reduced by hydrogen when in contact with copper; or (4) the precipitated oxides of the subscale may be complex compounds such, perhaps, as SiO2.Cu2O, which are partially reduced by hydrogen. These possibilities have been examined, and it has been concluded that the first three and possibly the fourth are operative collectively or individually under more or less predictable conditions. Effect OF Precipitated Cuprous Oxide and Dissolved Oxygen The literature provides no definite proof that oxygen in solid solution in copper can confer susceptibility to hydrogen embrittlement; indeed, the research of Leiter2 seemed to indicate the opposite—that to produce the effect, cuprous oxide must be present in massive form and in a more or less continuous network along the grain boundaries. To test this point, pure copper has been annealed in hydrogen under conditions designed to ensure the presence in various samples of: (I) precipitated cuprous oxide, (2) dissolved oxygen only, and (3) no oxygen in any form. Very pure copper" said to contain no oxygen and no spectro-scopically detectable traces of any other element (that is, no individual detectable impurity in quantity greater than 0.0001 per cent) was used. Strips of this material cold.-rolled 75 per cent to 1/8 in. in thickness were subjected to the following treatments, the results of which are noted:

Jan 1, 1941

By Frederick N. Rhines, William A. Anderson

The investigations of Wymanl have demonstrated that copper deoxidized with several of the commonly used agents that confer immunily to ordinary hydrogen em-brittlement can still be embrittled if it is annealed alternately under oxidizing and reducing conditions. During the oxidizing cycle, oxygen diffuses into the copper and frequently deposits a subscale composed of the oxide of the residual deoxidizing agent. Upon subsequent reduction with hot hydrogen, the copper becomes ruptured along the grain boundaries to a depth sharply limited by the previous penetration of oxygen as delineated by the inner boundary of the subscale. Obviously the sensitivity to this kind of hydrogen embrittlement is engendered by the introduction of oxygen during the oxidizing anneal, but beyond this the mechanism of the process, and hence the controlling factors, remain obscure. There are several possibilities: (I) oxygen dissolved in the copper matrix of the subscale may, upon cooling prior to the hydrogen anneal, precipitate as cuprous oxide which is subsequently reduced by hydrogen as in the familiar case of hydrogen embrittlement; (2) oxygen in solid solution in copper may itself confer susceptibility to embrittlement by hydrogen; (3) the normally refractory oxides such as those of aluminum, silicon and titanium may themselves be reduced by hydrogen when in contact with copper; or (4) the precipitated oxides of the subscale may be complex compounds such, perhaps, as SiO2.Cu2O, which are partially reduced by hydrogen. These possibilities have been examined, and it has been concluded that the first three and possibly the fourth are operative collectively or individually under more or less predictable conditions. Effect OF Precipitated Cuprous Oxide and Dissolved Oxygen The literature provides no definite proof that oxygen in solid solution in copper can confer susceptibility to hydrogen embrittlement; indeed, the research of Leiter2 seemed to indicate the opposite—that to produce the effect, cuprous oxide must be present in massive form and in a more or less continuous network along the grain boundaries. To test this point, pure copper has been annealed in hydrogen under conditions designed to ensure the presence in various samples of: (I) precipitated cuprous oxide, (2) dissolved oxygen only, and (3) no oxygen in any form. Very pure copper" said to contain no oxygen and no spectro-scopically detectable traces of any other element (that is, no individual detectable impurity in quantity greater than 0.0001 per cent) was used. Strips of this material cold.-rolled 75 per cent to 1/8 in. in thickness were subjected to the following treatments, the results of which are noted:

Jan 1, 1941

By Herbert Clark Hoover, Lou Henry Hoover

THE third book has explained the various and manifold varieties of veins and stringers. This fourth book will deal with mining areas and the method of delimiting them, and will then pass on to the officials who are connected with mining affairs'. Now the miner, if the vein he has uncovered is to his liking, first of all goes to the Bergmeister to request to be granted a right to mine, this official's special function and office being to adjudicate in respect of the mines. And so to the first man who has discovered the vein the Bergmeister awards the head meer, and to others the remaining meers, in the order in which each makes his application. The size of a meer is measured by fathoms, which for miners are reckoned at six feet each. The length, in fact, is that of a man's extended arms and hands measured across his chest ; but different peoples assign to it different lengths,

Jan 1, 1950

By Paul M. Tyler

MARKETWISE the year 1935 was rather a good one for most of the rare and minor metals; as a class they climbed out of the depression much faster than the common metals. The diamond market, too, was better than it had been for years, attributable only in part to investment buying, as there was a genuine pick-up in consumer demand. Wars and rumors of war tended to speed up purchases of certain metals, but consumption for peaceful purposes was the principal factor. Significant was the important role played by new industrial uses. New discoveries during the year were disappointingly few, considering the broad extent of this research frontier. Scientific developments were far from being at a stand-still, of course, but the dominant note was the cashing in on research consummated in former years. With even a moderate upturn in general business a surprising number of laboratory ideas donned overalls and found jobs in industry.

Jan 1, 1936

By Harlowe Hardinge

[Crushing Tests by Pressure and Impact (T.P. 1895, by F. C. BOND,, Min. Tech. Jan. 1946). Discussion by H. HARDINGE and the author 1 Pumping Sands, Slurries and Slimes and Installation and Performance of Sand Pumps (T.P. 2013, by W. B. STEPHENSON, Min. Tech., May 1946 and T.P. 1978, by C. G. SOUTHMAYD, Min. Tech., March 1946). Discussion by OSCAR LEE, G. J. HOLT, L. D. ANDERSON, and the author 2 Rapid Polarographic Method for Determination of Copper, Zinc and Lead in Flotation Tailings (T.P. 2010, by G. A. CROWE and W. T. BISHOP, Min. Tech., March 1946). Discussion by E. H. ROSE and the authors 4 Ball Wear and Functioning of the Ball Load in a Fine-grinding Ball Mill (T.P. 1984, by W. I. GARMS and J. L. STEVENS, Min. Tech., March 1946). Discussion by J. F. MYERS, E. W. DAVIS, F. M. JARDINE, H. HARDINGE, F. C. BOND and the authors 5 Correlation between Mineral Behavior in Cataphoresis and Flotation (T.P. 2005, by A. M. GAUDIN and S. C. SuN, Min. Tech., May 1946). Discussion by 0. C. RALSTON, G. L. SIMARD and D. J. SALLEY 7 Accident Experience in Milling (T.P. 1981, by J. F. MYERS and S. E. SHARP, Min. Tech., May 1946). Discussion by C. E. MCKNIGHT, C. H. BENEDICT, T. S. WILSON and S. POWER WARREN9 Mill Design for Labor Economy (T.P. 1997, by NORMAN WEISS, Min. Tech., May 1946). Discussion by R. S. HANDY and the author13] Crushing Tests by Pressure and Impact (0.C. Ralston presiding) HARLOWE HARDINGE.*-Has the impact method described in the paper been used to compare the resistance to reduction in size of various materials with actual operation results of mills in the field? Is this impact method a better index of the true resistance to grinding under actual field conditions than other methods the author has reported in the TRANSACTIONS? F. C. BOND (author's reply).-The impact crushing device was designed to measure relative resistance to crushing, or what may be called the crushability, and is not used for comparing the resistance to grinding, or grindability. The correlation between crushability and grindability of different materials is not at all close, since fractures, zones of weakness, and structural features of rock have a much greater effect upon the crushability than upon the grindability. We still depend upon our standard grindability tests for measuring resistance to grinding, and use the impact crushing tests only in relation to crusher installations. The impact crushing device has several advantages over the measurement of crushing strength in pounds per square inch as an index of crushing resistance.

Jan 1, 1946

By H. W. McQuaid, E. W. Ehn

It is usually assumed that chemical specifications are sufficient for steel to be used for case carburizing, and if the steel analyzes within the ordinary limits specified for steel for this purpose, no difficulty traceable to the steel used should be encountered in obtaining satisfactory results in the case carburizing and hardening. Much work has been done to determine the effect of various alloying elements on the rate of carbon penetration, etc. but, to our knowledge, little if anything has been published in regard to the effeet of the quality of the steel on the final results in the hardening of case-carburized steel parts. The writers believe that the structure of the case both before and after quenching is greatly affected by the actual condition of the steel itself as made, and that for good results in the case-carburizing and hardening departments, the steel should be of the best possible quality as regards non-metallic impurities. It is the purpose of this paper to prove that the presence of excess dissolved oxides in the steel, as made in the melting furnace, affects permanently the results obtained in carburizing and hardening and that it is possible that the presence of dissolved oxide call result in total unfit-ness of low-carbon steel for case hardening purposes. When races and rolls for roller bearings are made from a low-carbon steel, case carburized and hardened, it is of primary importance that the results of this treatment be of the highest quality. It is necessary, therefore, that in the case-carburizing work each detail be rigorously checked to avoid any defects which would cause the loss of much time and material. The case carburizing with which this paper deals was done in under-fired oil furnaces. The temperature of each furnace is controlled by means of a platinum platinum-rhodium thermocouple, in connection with a potentiometer indicator and potentiometer recorder. The temperature of each furnace is registered every 15 min. by an operator, who is continually checked by the automatic recorders.

Jan 1, 1922

By H. W. McQuaid, E. W. Ehn

It is usually assumed that chemical specifications are sufficient for steel to be used for case carburizing, and if the steel analyzes within the ordinary limits specified for steel for this purpose, no difficulty traceable to the steel used should be encountered in obtaining satisfactory results in the case carburizing and hardening. Much work has been done to determine the effect of various alloying elements on the rate of carbon penetration, etc. but, to our knowledge, little if anything has been published in regard to the effeet of the quality of the steel on the final results in the hardening of case-carburized steel parts. The writers believe that the structure of the case both before and after quenching is greatly affected by the actual condition of the steel itself as made, and that for good results in the case-carburizing and hardening departments, the steel should be of the best possible quality as regards non-metallic impurities. It is the purpose of this paper to prove that the presence of excess dissolved oxides in the steel, as made in the melting furnace, affects permanently the results obtained in carburizing and hardening and that it is possible that the presence of dissolved oxide call result in total unfit-ness of low-carbon steel for case hardening purposes. When races and rolls for roller bearings are made from a low-carbon steel, case carburized and hardened, it is of primary importance that the results of this treatment be of the highest quality. It is necessary, therefore, that in the case-carburizing work each detail be rigorously checked to avoid any defects which would cause the loss of much time and material. The case carburizing with which this paper deals was done in under-fired oil furnaces. The temperature of each furnace is controlled by means of a platinum platinum-rhodium thermocouple, in connection with a potentiometer indicator and potentiometer recorder. The temperature of each furnace is registered every 15 min. by an operator, who is continually checked by the automatic recorders.

Jan 1, 1922

By Frank V. Hicks

THE following paper-in no sense a technical paper-is a summary of a safety campaign instituted by a coal-mining company to improve an unfortunate safety record. The experience should be suggestive equally to coal and metal-mining companies. With few precedents to follow in the beginning, the course was charted by trial and error. The endeavor, often disheartening, finally resulted in the capture of the most coveted safety trophy in the mining industry, "The Sentinels of Safety," awarded by the Hercules Powder Co. of Wilmington, Del., through the U. S. Bureau of Mines. The period described covers the 10-year interval, 1924 to 1933, the year 1933 being that for which the award was made. The coal company considered has produced annually for a number of years an average of 2,750,000 tons of coal, employing at various times from 1.800 to 3000 men. Prior to 1924, the

Jan 1, 1935

By Richard McCaffery

WHEN we began the study of blast furnace slags we limited our work at first to a study of those slags containing only lime, alumina and silica. On our paper1 on some of the results of this first work, the solubility of sulfur in slags containing no magnesia was reported and the question of sulfur solubility and slag viscosity discussed. There has been, for a long time, a very great difference of opinion among metallurgists as to he effect of magnesia in blast furnace slags, and the literature is full if expressions of the most contrary opinions on the subject. As a result, our next publication' developed the constitution of slags considered as a four-component system, silica-alumina-lime-magnesia, and advanced an explanation of slag structure which accorded with the facts and with scientific theory. The present paper continues our study of the general subject of slags. As blast furnace slags are included in the silica-alumina-lime-magnesia system, which is a particular case of four-component solutions, we have determined that there are 22 components Table 1), which may enter into the silica-alumina-lime-magnesia system and that 10 or 12 of these components may be present in blast furnace slags which are within the ordinary ranges of composition. To cave a very definite conception of the behavior of these components in a slag, we have developed the theory of the cooling of a four-component solution from the liquid state to the solid and the conclusions that we obtained have been made use of in this paper. On account of the importance of the four oxides and 18 compounds which enter into the silica-alumina-lime-magnesia system, some method of calculating the percentages of the various compounds that are present in the slag when the percentages of the oxides are given, seemed very desirable and we develop L method later herein for doing this, and finally we give illustrations of the composition of a wide series of blast furnace slags and show some applications of these composition data.

Jan 1, 1927

By M. F. Trice

Pyrophyllite is a hydrous aluminum silicate (A1²Si4O10(OH)²)1 that, occurs in both the foliated and the massive forms. The foliated variety resembles talc in that it has a greasy feel, a pearly luster, perfect basal cleavage, and usually is white, although in some deposits apple green, gray, brown, russet, and nearly black specimens may be found. The massive deposits of pyrophyllite yield pearl gray to light tan aggregates, some of which are so friable that they may be crushed with the hands into a fine gritty powder. Frequently specimens of the massive variety are studded with crystals of radial structure. The mineral has a specific gravity of about 2.7 and a hardness of 1 on Mohs' scale.' The chemical composition of commercial pyrophyllite reflects the mineralogy of the deposits, which, according to Stuckey12 contain pyrophyllite and quartz, together with chloritoid, sericite, and a few other minerals of negligible importance. The latter, he says, ('are noticed in but small quantities to the extent they might occur as accessory constituents of an igneous rock or as products of regional metamorphism or weathering. . . . Quartz is abundant everywhere except in the very best grades of pyrophyllite." Analyses of specimens from several deposits are listed in Table 1, showing that the silica content varies from 57 to 73 per cent and the alumina from 22 to 33 per cent. Oxides of iron and the alkaline metals are collectively present, with one exception, to an extent of about 1 to 1.5 per cent. Sources At present, North Carolina is the only commercial source of pyrophyllite, although the mineral has been found in small quantities in many parts of the world. The North Carolina deposits are in the "Carolina Slate Belt," which traverses the center of the state in a southwesterly direction. This belt varies from 8 to 50 miles in width. Two major deposits of pyrophyllite lie along its eastern boundary, in what is known as the Deep

Jan 1, 1942

By M. F. Trice

Pyrophyllite is a hydrous aluminum silicate (A1²Si4O10(OH)²)1 that, occurs in both the foliated and the massive forms. The foliated variety resembles talc in that it has a greasy feel, a pearly luster, perfect basal cleavage, and usually is white, although in some deposits apple green, gray, brown, russet, and nearly black specimens may be found. The massive deposits of pyrophyllite yield pearl gray to light tan aggregates, some of which are so friable that they may be crushed with the hands into a fine gritty powder. Frequently specimens of the massive variety are studded with crystals of radial structure. The mineral has a specific gravity of about 2.7 and a hardness of 1 on Mohs' scale.' The chemical composition of commercial pyrophyllite reflects the mineralogy of the deposits, which, according to Stuckey12 contain pyrophyllite and quartz, together with chloritoid, sericite, and a few other minerals of negligible importance. The latter, he says, ('are noticed in but small quantities to the extent they might occur as accessory constituents of an igneous rock or as products of regional metamorphism or weathering. . . . Quartz is abundant everywhere except in the very best grades of pyrophyllite." Analyses of specimens from several deposits are listed in Table 1, showing that the silica content varies from 57 to 73 per cent and the alumina from 22 to 33 per cent. Oxides of iron and the alkaline metals are collectively present, with one exception, to an extent of about 1 to 1.5 per cent. Sources At present, North Carolina is the only commercial source of pyrophyllite, although the mineral has been found in small quantities in many parts of the world. The North Carolina deposits are in the "Carolina Slate Belt," which traverses the center of the state in a southwesterly direction. This belt varies from 8 to 50 miles in width. Two major deposits of pyrophyllite lie along its eastern boundary, in what is known as the Deep

Jan 1, 1942

By H.E. Brauer

Among the zinc base alloys used for casting in metal moulds, pnrticularly die casting, those alloys containing aluminum usually together with copper, are probably the most widely used. The reason lies in their desirable mechanical properties and the fluidity and absence of hot shortncss which facilitate ca,sting. Objection to the use of these alloys may be raised on account of the rather frequent instances of failure of a type variously described as disintegration, exfoliation and intererystalline corrosion. In all cases which have come to our kno~vlcdge where the conditionsof service were known, failure has occurred upon cxposurc to moisture and heat varying from a hot moist atmosphere to lligh pressure steam. RIoreover, the alloys described in all such roses contain impurities or alloying metals which the present authors have found to have enormous accelerating effects on intererystalline oxid:~t'ion in zinc-aluminurn alloys. Thus Williams1 experimented with an alloy containing a large percentage of tin exposed in Cuba. Baucr2 reports failure of a boiler plug containing over 1 per cent. of impurities, doubtless lead for the must part, and Rawdon's3 examinations were madc on an alloy containing 0.1 per cent. lead also exyosctl to thc Tropics. No thorough investigation of the nature and cause of this type of failure has been made heretofore, so far as the authors are aware, although Rawdon correctly classified it as internal oxidation. We have, therefore, carried out this investigation in order to det'ermine the exact nature of this phenonienon and the effect of other metals present as impurities or intentional additions in accelerating or retarding it. In the appendix we include a considerable amount of data which may be valuable in selecting an alloy combining good physical properties with high resistance to oxidation. At the time this work was undertaken the best available equilibrium *Investigator, Metal Section, Research Division, The New Jersey Zinc Company. 'H. W. Williams—Jour. Am. Inst. of AIet,als, Vol. 11, p. 221 (1917). 2o. Bauer—ZeiL, fiir i'vletall Kunde, Vol. 12, .No. 7, pp. 129-31 (1920). 3H. S. Rawdon—Trans. Am. Elcctrochcmic.al Society (1921).

Jan 1, 1923

By H. E. Brauer

Among the zinc base alloys used for casting in metal moulds, pnrticularly die casting, those alloys containing aluminum usually together with copper, are probably the most widely used. The reason lies in their desirable mechanical properties and the fluidity and absence of hot shortncss which facilitate ca,sting. Objection to the use of these alloys may be raised on account of the rather frequent instances of failure of a type variously described as disintegration, exfoliation and intererystalline corrosion. In all cases which have come to our kno~vlcdge where the conditionsof service were known, failure has occurred upon cxposurc to moisture and heat varying from a hot moist atmosphere to lligh pressure steam. RIoreover, the alloys described in all such roses contain impurities or alloying metals which the present authors have found to have enormous accelerating effects on intererystalline oxid:~t'ion in zinc-aluminurn alloys. Thus Williams1 experimented with an alloy containing a large percentage of tin exposed in Cuba. Baucr2 reports failure of a boiler plug containing over 1 per cent. of impurities, doubtless lead for the must part, and Rawdon's3 examinations were madc on an alloy containing 0.1 per cent. lead also exyosctl to thc Tropics. No thorough investigation of the nature and cause of this type of failure has been made heretofore, so far as the authors are aware, although Rawdon correctly classified it as internal oxidation. We have, therefore, carried out this investigation in order to det'ermine the exact nature of this phenonienon and the effect of other metals present as impurities or intentional additions in accelerating or retarding it. In the appendix we include a considerable amount of data which may be valuable in selecting an alloy combining good physical properties with high resistance to oxidation. At the time this work was undertaken the best available equilibrium *Investigator, Metal Section, Research Division, The New Jersey Zinc Company. 'H. W. Williams—Jour. Am. Inst. of AIet,als, Vol. 11, p. 221 (1917). 2o. Bauer—ZeiL, fiir i'vletall Kunde, Vol. 12, .No. 7, pp. 129-31 (1920). 3H. S. Rawdon—Trans. Am. Elcctrochcmic.al Society (1921).

Jan 1, 1923

By John McDonald

THIS report is a continuation of an earlier one with a similar title,1 to which the reader is referred for such details of procedure as do not appear here. A brief summary will be given of the objects and methods of the research at this time. It was pointed out in the previous paper that properties of magnesium alloys, as re-ported by different workers, often differ. This was thought to be due to differences in the preparation of the specimens tested. The ideal way to compare alloys would be to prepare each of them in so many ways that reasonable assurance would exist that the best properties of each alloy had been developed. The alloys would then be com-pared on the basis of these properties. The treatment actually given the alloys of these studies is necessarily a compromise with completeness. Nevertheless, enough treatments have been given so that a con-siderable degree of assurance exists that the properties obtained are representative of the alloy as such, and not merely of the manner in which it was worked and heat-treated.

Jan 1, 1940

By S. K. Basu, H. H. Kellogg

THE physical-chemical behavior of the system Pb-S-0 is of prime importance to the understanding of lead smelting processes, yet little accurate information is available on either equilibrium or kinetic behavior in this system. This paper is the first report of a program designed to fill gaps in our knowledge of this system. In the total ternary Pb-S-0, the region of greatest metallurgical interest is that bounded by the compositions Pb-PbS-PbS0,-PbO-Pb. Systems richer in sulfur, or richer in oxygen,* than those essentially pure SO2. This conclusion follows from the fact that all systems are in a highly reduced state, since either PbS or Pb is a constituent of all the equilibria. The content of 02, SO3, S2, S6, S8, and so forth, can be shown to be negligible compared to SO, in all such systems.* corresponding to this region can only be obtained at gas pressures exceeding 1 atm, a condition seldom met in lead smelting practice. Not only is the present study limited to condensed phases within this portion of the total system, but it is limited to temperatures at which all phases are pure solids, except for lead, which is liquid. In this limited system the following seven condensed phases are known to exist: Pb(l), PbS(c), PbO(c), PbSO,(c), PbSO,•PbO(c), PbSO4 • 2PbO(c), and PbSO, -4PbO(c). PbO exists in two crystal modifications,' but only the high-temperature yellow form is considered here. Schenck and co-workers2-4 reported the compound PbSO4 3Pb0 to be stable at high temperature, but the more recent work of Lander,5 and the present work, prove that the tetra-basic sulfate, rather than the tri-basic sulfate is stable. Fig. 1 shows the composition diagram for the binary PbO-PbSO2, based primarily on the work of Lander. In this study the univariant boundaries and invariant points existing among these seven condensed phases and the gas phase have been determined. In a ternary system, the phase rule indicates that an invariant point involves the simultaneous equilibrium of five phases—four condensed phases and the gas phase. A univariant relation involves four phases—three condensed phases and the gas phase. The gas phase in the systems studied is The following stable univariant equilibria between SOz and the condensed phases were identified: (a) PbS + 7PbS04 = 4(PbSO, - PbO) + 4SO2 (b) PbS + l0(PbS04 • PbO) = 7(PbSO4- 2PbO) + 4SO2 (c) PbS + 8(PbSO4 • 2PbO) = 5(PbSO4 . 4PbO) + 4SO2 (d) Pb + PbSO, • 4PbO = 6PbO + SO2 (e) 3PbS + PbSO4 . 4PbO = 8Pb + 4SO2 (f) 3PbS + 16(PbS04 PbO) = 7(PbSO4 . 4PbO)+ 12SO2 (g) 2PbS + PbSO,2PbO = 5Pb + 3SO2 (h) Pb + 3(PbSO4 . 2PbO) = 2(PbSO,. 4PbO) + SO, Of these eight univariant equilibria, five were measured in this work (a, b, c, d, and g) and the behavior of the other three (e, f, and h) was calculated by thermodynamic analysis of the measured data. Two invariant points were found corresponding to simultaneous equilibria as follows: Point 1: PbS, PbSO4PbO, PbSO4.2PbO, PbSO, - 4PbO, and SO2 Point 2: Pb, PbS, PbSO, . 2PbO, PbSO, - 4PbO, and SO2, From the measurements it was also possible to calculate the thermodynamic properties of the three basic sulfates of lead at 298.16°K. EXPERIMENTAL Apparatus—The experimental method consisted of the measurement of the gas pressure exerted by a given reaction mixture at a given temperature. An iridium crucible was used to contain the reaction mixture. There was no evidence of attack of the iridium,* but after use at high temperature for a week

Jan 1, 1961

By CHARLES COURT

I must tell you at the outset that I come to this conference deeply disturbed at the 'role of Government in international dealings in mineral and energy resources'. I am disturbed by- the confusion that now passes for policy. I am disturbed by the short- range view of critical problems taken by a majority of Governments. I am equally disturbed by the even shorter range of view taken by a growing army of industries. Many of them clamour for Governments to solve their problems in a specific way, with little regard for any other sector but their own-and with even less regard for the fact that every time a Government takes over some of their responsibilities they surrender some of their freedom. I would not say that longer range views don't exist. But I would say that they don't prevail at the present time. Instead, we are seeing the constant development of many policies for individual problems which don't tackle the fundamental causes. We must get back to basics without delay.

Jan 1, 1978

By J. L. Schroeder, W. G. Talman

EXPERIENCE has shown that certain known natural conditions and other indefinite characteristics combine to make a mining area vulnerable to mountain bumps. Some of the known conditions are heavy overburden, an overlying stratum of strong non-elastic rock, a structurally strong coal seam that does not crush easily and yet is the weakest stratum in the series, and a floor stratum of more than ordinary firmness. The indefinite characteristics could include resistance of top or bottom of a coal seam to lateral flow, effect of immediate top and bottom strata, nature of the coal seam, and other factors about which very little is known. It is in this area that exhaustive study is needed to achieve positive control of the dreaded mountain bump hazard. In the Gary district, West Virginia, two of the five operating mines have areas known to be vulnerable to mountain bumps.These are the No. 2 and 6 mines, which are working the Pocahontas No. 4 coal seam. In this area the seam is overlain at a zero to 10-ft interval by the massive Eckman sandstone, which is about 100 ft thick in the vulnerable areas. Total overburden, consisting of shale, coal seams, and sandstones, ranges from 700 to 1400 ft where bumps have occurred (Fig. 1). The coal seam is 4 to 8 ft thick and has a weak columnar structure of very soft and spongy or woody coal. The immediate top is either the Eckman sandstone or hard shale, both of which provide generally good roof conditions for mining operations. The bottom ranges from medium to hard gray shale. The incidence of bumps in the Gary district dates from about 1930 and can be correlated to some degree with the increased rate of extraction attained with mechanical mining. During early years of operation at the No. 2 and 6 mines, most of the work was development and under comparatively light cover. As overburden became heavier, together with an increasing percentage of coal coming from pillar extraction, mountain bumps began to occur. Before 1945 they were much less severe than in later years, and because there were no injuries or fatalities, no records were kept. But by 1951 the incidence of bumps had increased to such extent that it became evident a mining system would have to be designed to eliminate or at least minimize these occurrences. Drawing on experience with modified versions of old systems and certain characteristics peculiar to the Pocahontas No. 4 coal seam, the district mining engineer, Martin Hayduk, outlined the essential factors for bump control in the Gary district. These control factors indicated: 1) The highly stressed area, which lies within the limits of convergence effects, moves at approximately the same rate as the retreating pillar line. 2) There is a decided softening of the periphery of blocks which is greatest and deepest on the gob side. 3) Blocks less than 45 ft wide never have been known to bump in the Pocahontas seams. Fig. 2 shows the mining plan based on these observations—a thin-pillar system with a minimum of secondary development. It was recognized from the start that the Hayduk system had certain limitations. When pillar work backed up to an inevitable surrounded block it was no longer applicable; also, burnt bottom and/or unknown factors reduced the system's effectiveness in certain headings. Since there was no way to eliminate the loaded block, it was decided to experiment with auger drilling to attain controlled release of this stored-up energy. The decision to auger was made after consideration of three separate plants, which were: 1) To cut the solid block into pillars of maximum size by driving away from the fracture line and at such a distance outby that development

Jan 1, 1959

By Robert Mehl

THE purpose of this investigation was to prepare high-purity iron-carbon alloys, to determine as precisely as possible the A3(GOS), the Acm(SE), and the A1(PSK) transformation temperatures in the meta-stable iron-iron carbide system (up to 1.4 per cent C), and to study the influence of carefully controlled and constant rates of heating and cooling (1/8 to 2° C. per minute) upon the transformation temperature and upon the resulting microstructure. Apart from the general metallurgical importance attending the completion of such a task, it will be noted that highly precise transformation temperatures are of interest and importance in the thermodynamic study of this system1. Several determinations of the iron-iron carbide diagram have been made. These suffer generally from the low purity of the alloys used, and from the application of methods of investigation of low sensitivity. Attempts to compare and weight the many data available in an effort to construct as accurate a diagram as possible have, in the main, been unsuccessful. In general, the wide differences in the results of different workers, the lack of complete analytical data, the omission of important details relating to the heat-treatment of the alloys, and the meager description of the methods of investigation applied, render such a process of averaging nearly meaningless. It may be seen from the summaries by Epstein2 and Körber and Oelsen1 that variations as great as 30° C. exist in the reported data on the A3 temperatures in iron-carbon alloys. For-tunately, the A3 temperature in pure iron is now known to be 910° C. ± 1° C.3 The best recent work on iron-carbon alloys is that of Esser4 on hypoeutectoid steels and that of Sato' on both hypoeutectoid and hyper-eutectoid steels.

Jan 1, 1937

By W. C. Clark, J. B. Schloen

Two papers have been written, previously concerning operations at the Montreal East plant of Canadian Copper Refiners Limited. The first one,' written in 1932, described silver-refinery operations at the time for producing silver and gold bullion from tankhouse anode slimes; the second,Z published in 1933, consisted of a description of the entire plant. Since publication of these papers the refinery has become the world's largest producer of refined selenium. The first selenium was produced in August 1934. Tellurium production on a commercial scale followed in October 1935. This paper will deal with selenium and tellurium production and also with present operations in the silver refinery. Blister cakes from Hudson Bay Mining and Smelting Co., Flin Flon, Manitoba, and commercial anodes from Noranda Mines Limited, Noranda, Quebec, are refined at Montreal East. Both these bullions have unusually high gold, selenium and tellurium content. The average assay of raw slimes produced from domestic and Noranda anodes is about 40 per cent Cu, 3600 oz. per ton Ag, 800 ox. per ton Au, 22 per cent Se and 3.7 per cent Te. Early Silver-refinery Operations From the start of operations in 1931 until July 1934, the raw slimes were oxidiae-roasted at 700' F. in a Nichols-Herreshoff furnace, acid-leached with tankhouse discarded foul electrolyte (20 per cent HzSOa), filtered and charged directly to the dor6 furnace for refining to dore metal. This is the customary method for treating tankhouse anode slimes but was not suitable at the Montreal East plant because of the high selenium and tellurium content of our slimes. In the acid-leaching process about 50 per cent of the selenium and tellurium in the roasted slimes was dissolved in the electrolyte. These elements were recovered with the copper as a sludge in a small electrolytic

Jan 1, 1944