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By Emma Smith, R. W. Guard

INVESTIGATION of the nickel-rich end of the Ni-Zr system has been prompted by an interest in the effect of small amounts of zirconium in high temperature alloys. Hansenl presents a hypothetical diagram based on the work of Allibone and Sykes,2 who investigated the system up to 44 atomic pct (55 wt pct) Zr by metallographic means. Since the alloys they used were melted in Alundum crucibles they were probably contaminated with appreciable amounts of aluminum. They found two compounds which they called Ni3Zr and Ni4Zr. Hayes, Roberson, and Paasche3 identified a compound NiZr (50 atomic pct Zr) with a melting point of 1470°C. Such a high melting compound is not compatible with the observation of Allibone and Sykes2 hat a eutectic is formed near 50 atomic pct. The alloys containing up to 60 atomic pct Zr were melted in an inert atmosphere in a noncon-sumable electrode arc furnace. Analysis of most of the alloys indicated negligible loss of zirconium. The alloys were examined in the as-cast condition and also after annealing for 6 hr at 1175°C (or 1000°C for the alloys between 25 atomic pct and 45 atomic pct). Metallographic specimens were etched using mixtures of HF-HNO3-H2O or acetic acid- HN0,-H,O. The specimens for the solidus determinations were wrapped in molybdenum foil and sealed in evacuated quartz tubes. Specimens to be heated above 1300°C were enclosed in zirconia tubes inside the quartz to prevent reaction with molybdenum. The solidus determinations were carried out by heating the specimens at various temperatures for a few minutes and then examining the interior structure metallographically to determine at what temperature melting began. The 150 mesh powders for X-ray analysis were annealed in an evacuated quartz tube for 2 hr at 540 °C to remove cold work. Alloys with 22.5 atomic pct Zr and 44.4 atomic pct Zr required annealing at 700 °C for complete recovery. The grains of both of these alloys were soft and rather ductile. Both Debye-Scherrer film patterns and spectrometer traces were made for each alloy using filtered copper radiation. Results and Discussion The presence of a substantial amount of second phase in an alloy with 1.1 atomic pct Zr indicated that the solid solubility of zirconium in nickel is somewhat less than 1 atomic pct. The a0 value for the face-centered-cubic matrix in the same alloy was equal to that of pure nickel, so that the solubility must be very small. This observation is as expected from the large atom size difference. Annealed specimens of alloys with 15.0, 16.7, 22.5, 28.6, 44.4, and 59.4 atomic pct Zr showed. micro-structures that were essentially single phase. When

Jan 1, 1958

By J. J. Beeson

Page I. PrimaRy MineRalization............................................ 356 1. Introduction..................................................... 356 a. Scope of Work............................................... 356 6. Acknowledgments............................................ 357 c. The Bingham Mining District.................................. 357 d. General Geology.............................................. 357 e. The Utah Copper Mine....................................... 376 f. Field and Laboratory work.................................... 376 2. The Quartz-Monzonite.............................................. 377 3. The Pegmatite Veins.....:.•..............................:........ 378 4. The High-Temperiture Veins.........................-.............:379 5. The Early Hydrotherma! Period.:......................'............ 380 6. The Late Hydrothermal Period................................:.... 385 II. Seconuabx EnricuMENT............................................. 386 . 1. Author's Note;..... ;............................................ 386 2. Factors Governing Enrichment.....................................: 387 3. The Enrichment.................................................... 387 4. The Covellite Enrichment.; .:; ; : .:. :..:.............:................ 388 a. The Capping above the Covellite Ores:....:....................... 388 b. Conclusions Drawn. from a Study of the Capping and the Covellite ; Ores....,.............................................:.....,.' 392 c. Covellite Enrichment at Depth......:......................... : : 392 5. The Chalcocite Enrichment...................................... ; 394 a. The Carbonates in the Capping above .the Chalcocite Ores...:..: .. 394 ' b. The Formation of Chalcocite..:.:. :......:..'...........,......' 394 . 6. Secondary Chalcopyrite and Bornite.............................i ..., . 395 111.- Conclusions as to the Formation.oF the ImpoRtant Sulphides in the Disseminated ORes........................................,.......... 400 I. Primary MiNeRalization 1. Intrdtiction a. Scop. e .of Work.. first part bf, this paper deals with the country rock, its pegihatitic, pneumatolytic', and hydrothermal altektions; also, the effect of magnetite on the deposition of the primary chalcopyrite and pyrite.

Jan 1, 1916

AlFred JamEs," London, Eug.:—I thank you, gentlemen, for Sour kind invitation to address you. It is a very great pleasure for me to be here at your annual meeting, and, although I have been a member since 1894, this is the first opportunity I have

Jan 1, 1909

By W. T. Turrall, D. Porter

The paper describes a machine developed for the purpose of concentrating clear optical grade fluorspar crystal from a feed material containing less than 1 pct impurities. The principle of concentration is based on the fact that in a liquid having an index of refraction equal to that of fluorite (n — 1.434) clear crystals are invisible, whereas crystals containing occluded impurities absorb a part of the light. As the crystals pass through a light beam, undesired crystals give themselves away by creating a shadow on a photoelectric receiver. .The shadow is converted by the photoelectric cell into an electric pulse. An electronic circuit amplifies this pulse and commands the operation of a mechanical concentrator. Hp HE crystal laboratory, Dept. of Physics, Massa--*- chusetts lnstitute of Technology, was confronted with the problem of obtaining a supply of optical grade calcium fluoride (CaF,) for use in growing synthetic CaF, crystals. A search of the known fluorspar deposits did not indicate that any quantity of optical spar could be obtained. Even the best material had to be sorted by hand to remove impurities. The process for growing CaF, crystals developed by Professor D. C. Stockbarger of the Dept. of Physics, M.I.T., necessitates very pure feed materials. Exclusion of impurities is required, even in amounts detectable only spectrographically. The impurities occurred as minute inclusions of SiO,, BaSO,, CaCO,, FeS2, water or air. Crystals up to 4 in. in diam and weighing several pounds are made by the Harshaw Chemical Co. in Cleveland. Since the time required to grow a 4-in. crystal is about one week, and since the cost of manufacture is high, removal of impurities by any concentration method appeared practical. The mineral engineering section of the Dept. of Metallurgy undertook to investigate the possibility of concentrating clear optical fluorspar, —4 mesh + 10 mesh, from a feed containing over 99 pct CaF,. Various innovations of the known methods of concentration were considered, but in each case the minute amount of impurities associated with the crystal produced such extremely small differences

Jan 1, 1953

By W. T. Turrall, D. Porter

The paper describes a machine developed for the purpose of concentrating clear optical grade fluorspar crystal from a feed material containing less than 1 pct impurities. The principle of concentration is based on the fact that in a liquid having an index of refraction equal to that of fluorite (n — 1.434) clear crystals are invisible, whereas crystals containing occluded impurities absorb a part of the light. As the crystals pass through a light beam, undesired crystals give themselves away by creating a shadow on a photoelectric receiver. .The shadow is converted by the photoelectric cell into an electric pulse. An electronic circuit amplifies this pulse and commands the operation of a mechanical concentrator. Hp HE crystal laboratory, Dept. of Physics, Massa--*- chusetts lnstitute of Technology, was confronted with the problem of obtaining a supply of optical grade calcium fluoride (CaF,) for use in growing synthetic CaF, crystals. A search of the known fluorspar deposits did not indicate that any quantity of optical spar could be obtained. Even the best material had to be sorted by hand to remove impurities. The process for growing CaF, crystals developed by Professor D. C. Stockbarger of the Dept. of Physics, M.I.T., necessitates very pure feed materials. Exclusion of impurities is required, even in amounts detectable only spectrographically. The impurities occurred as minute inclusions of SiO,, BaSO,, CaCO,, FeS2, water or air. Crystals up to 4 in. in diam and weighing several pounds are made by the Harshaw Chemical Co. in Cleveland. Since the time required to grow a 4-in. crystal is about one week, and since the cost of manufacture is high, removal of impurities by any concentration method appeared practical. The mineral engineering section of the Dept. of Metallurgy undertook to investigate the possibility of concentrating clear optical fluorspar, —4 mesh + 10 mesh, from a feed containing over 99 pct CaF,. Various innovations of the known methods of concentration were considered, but in each case the minute amount of impurities associated with the crystal produced such extremely small differences

Jan 1, 1953

By Harrison Souder

MAGNETITE mining and milling in the Eastern States showed continuing improvement during the year. Some of the smaller mines remained idle, but the larger operations responded promptly to the improved situation in the iron and steel industry. The output of ore for 1936 was over twice that for 1935. A number of improvements were made in mine plant and equipment, and operating forces were increased and maintained at near normal. The coming year should see additional mines started up and production increased at the larger properties.

Jan 1, 1937

By Basil B. Zavoico

ALTHOUGH the American petroleum industry was affected by the Second World War from its early beginning it was not until Dec. 7, 1941- that the industry was placed on full war footing. Even throughout most of 1942 the American overseas operations were limited and not until late in the year did expansion of military activities, more particularly the offensive in North Africa, affect the domestic supplies to such an extent that critical deficiencies developed locally in this country, particularly along the East Coast. The definite outlook for greatly expanded offensive operations by the United States on both Atlantic and Pacific fronts makes certain that during 1943 the domestic situation will. not be alleviated; rather it may become even more critical even though additional transportation facilities, now being built and planned. will be completed from the southwestern producing states to the East Coast.

Jan 1, 1943

By William B. Plank

IN my studies during the past twenty years of the enrollments in the mining and metallurgical schools of the United States and Canada, I have been struck with the great diversity in the curricula offered by these schools. In 1933 when I made my first complete study of the schools (Mining and Metallurgy, May 1934, p. 211), I discovered 19 different curricula or programs of study, leading to almost as many different bachelor degrees, in the 49 schools in the United States and the 4 schools in Canada. These were: (1) Mining Engineering, (2) Coal Mining, (3) Metal Mining, (4) General Mining, (5) Mining Administration, (6) Mining and Metallurgy, (7) Metallurgical Engineering, (8) Metallurgy, (9) Petroleum Engineering, (10) Petroleum Refining, (11) Petroleum Geology, (12) Petroleum and Natural Gas, (13) Ceramic Engineering, (14) Ceramics, (15) Geological Engineering, (16) Mining Geology, (17) Economic Geology, (18) Geo- physics, (19) Fuel Technology.

Jan 3, 1950

By L. W. Rowe, W. R. Opie

A brief history of TiCI, production and purification is given. Chlorinator feed materials for the production of TiCI4 are classified. The thermodynamics and kinetics of Ticl4 production by chlorination of TiO2 are discussed. Problems encountered in the chlorination and purification steps are outlined in detail. MOST of the current processes for the production of titanium metal require the use of TiC14 as a source of titanium values. This material can only be produced by a dry chlorination process, since it is immediately hydrolyzed in the presence of water. When pure, the tetrachloride is a colorless liquid boiling at 136°C. It fumes readily in moist air, reacting immediately with the moisture to form TiO, and HC1. History The tetrachloride was prepared as early as 1826 by DumasL who chlorinated a red hot mixture of carbon and TiO,. Since then, numerous other mixtures have been used including rutile, ilmenite, beneficiated ilmenites, titanium pigment, slags, and the various titanium metalloids such as TiN, TiCN, TiOC, and TiS2. S2Cl2, phosgene, and CC14 have been substituted for chlorine and CO has been used in place of carbon.

Jan 1, 1956

INDEX TO TRANSACTIONS After a delay of many months, which is very much regretted, but which, it is hoped, will be one means of insuring a volume of accuracy where accuracy is very important, the Institute now has for distribution copies of the index of Volumes XXXVI to LV, inclusive. This is more than a mere index off names of authors and titles of papers. Every important topic under consideration by author or discusser is introduced under such key-word as will enable an engineer to locate the desired information with the minimum expenditure of time. This index sells for $5* in half morocco binding and $4*. in paper covers. With the index of Volumes II to XXXV (which sells for $5 in half morocco and $4 in paper covers), it forms a complete index of the first fifty-five volumes of the Institute's Transactions. These collective indexes are very valuable to members of the Institute, enabling them to look up matters in their own library; if they have the volumes to which the indexes refer, they can get the information at once, and, if not, they can readily determine whether or not a visit to a nearby public library is desirable.

Jan 7, 1918

J. Chipman (Massachusetts Institute of Technology, Cambridge, Mass.)—The fact that the experimental work has been applied to copper rather than iron and that the paper is presented to the Iron and Steel Division, I regard as rather significant. It shows the unity of metallurgy and the fallacy of trying to cut it up by metals. This result for the solubility of sulphur in molten copper correlates with Professor Schuhmann's finding that the published data on the other side of the copper-sulphur miscibility gap are also in error. I should like to ask the author to say a little bit more about the sulphur capacity of the slag. T. Rosenqvist (author's reply)-—I hope that Dr. Chipman will find the derivation of the expression for sulphur capacity more clearly explained in the printed version of the paper than in the oral discussion at the meeting. I feel that this quantity, which actually is the ratio of two activities, can be measured more easily than the individual activities. Even if the ratio CaO/CaS is chosen as the standard state, the expression can be used for any slag, even for slags completely free of lime, and it represents a way to put the desulphurizing power of all slag constituents into one bag. Some doubt has been expressed as to whether oxygen ions really exist in calcium oxide and in molten slags. From a thermodynamic view point that question is of minor importance. The term oxygen ion activity, or any activity for that matter, is defined rigorously by the equation: activity = exp u/RT, where u is the change in free energy connected with the transfer of one mol of ions from the standard state into the slag. Whatever happens to the ion in the slag is of no concern to the thermodynamicist. Regardless of whether the ion is "free" in the slag or not, or whether it is present in a very small amount, its activity can always be expressed, and for a thermo- dynamic calculation that is all we need. However, ionic activities will only be of some real value if they are simple functions of the slag composition, or can be measured easily. Concerning the real nature of the oxygen in the slag, my feeling is that the oxygen atom has a rather multiplex nature depending on how strongly it is tied by covalent forces or polarized by the other atoms or ions present. The oxides of iron, cobalt, and nickel differ from calcium oxide and blast furnace slags as to the amount of free electrons that can give rise to electronic conductivity. In slags we know that the conductivity is mostly ionic. The fact that reversible emf's can be obtained with oxygen electrodes in certain salt melts, indicates a significant amount of oxygen ions in these melts. But extended work, e.g. polaragraphic studies and measurements of transference number; are needed to obtain quantitative information about the real structure of the slags. D. E. Babcock (Republic Steel Corp., Youngstown, Ohio)—-With reference to the ion, it might be well to remember Dr. Moses Gomberg. All of his life he had no use for the ionization theory and he contributed greatly to the field of chemistry on the assumption there was no such thing as ions. I do not think we have to worry about whether the oxygen is ionic or not. I think one thing specifically should be brought to your attention and this I think is one of the important contributions of Dr. Rosenqvist. He pointed out what we know as oxygen potentials or what is described as oxygen potentials. I have used this concept for a long period of time and I want to state that if this concept is properly applied, it vitiates much of what we have in the literature, or makes our usual ideas regarding oxidation seem primitive. That one thing is more valuable than almost all the rest of the discussion as a fundamental basis on which to build a reasonable in-

Jan 1, 1952

By R. Q. Shotts

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

Jan 1, 1962

By H. Pew, J. H. Field

To alleviate pollution more restrictive legislation is being enacted, either limiting emission of pollutants or the type of fuel that can be utilized. The nature and magnitude of air pollution problems affecting the mining, preparation, coking and combustion of coal are described. Methods for combatting particulate emissions by use of mechanical separators and electrostatic pre-cipitors are discussed. Proposed methods to meet the problem of gaseous emissions currently receiving considerable attention are described, with special emphasis on methods to decrease pollution by sulfur oxides. Concern about air pollution goes back several centuries, but until very recently most effort has been aimed at coal smoke and other visible pollutants. The classic example of a 'successful' campaign for smoke abatement and control is the fruitful combined effort of the city of Pittsburgh and its surrounding Allegheny County, which eventually led to the reconstruction of downtown Pittsburgh at an estimated cost of one billion dollars. Historically, the city's downtown Golden Triangle district had been afflicted by pollutants evolving from steel mills, from a variety of other industries, and from railroad locomotives. Efforts to alleviate the situation prior to 1943 were virtually ineffective. In 1945, however, a comprehensive redevelopment plan was prepared and backed by state authority. Within a few years a clean, modern metropolis has evolved where once stood America's famous 'smoky city.' But the victory in Pittsburgh, as in various other American cities, has not solved the national problem. Current estimates indicate that 133 million tons annually of air pollutants from all sources still are emitted annually into the atmosphere above the United States. About 10% of this annual effluent is particulate matter so that most of the remaining pollution problems will be solved only when other effluents are reduced. Essentially, these are sulfur oxides, nitro- gen oxides, hydrocarbons, and carbon monoxide. Over the years, both states and local communities have tended to increase the restrictions on smoke and fly ash — problems mostly of concern in the combustion of coal. Prior to the middle 1950's, ordinances sometimes permitted emissions of smoke equivalent to as much as No. 3 on the Ringlemann scale. Since 1956, no ordinance has been passed which allows smoke of greater than No. 2. Under today's conditions of improved fuels, equipment and practice, a few communities have passed laws prohibiting emission of smoke of any density darker than Ringlemann No. 1. The majority of existing laws on fly ash emission in the U.S. limit emissions equivalent to 0.85 lb of fly ash per 1000 Ib of flue gas. In recent years, however, regulations which have been adopted give cognizance to the higher level of performance now obtainable with improved equipment. A comparison of the restrictions of five codes adopted since 1960 is given in Table I. The most stringent of these is the one for New York City which provides for a maximum emission of 0.6 lb fly ash per million Btu heat release (equivalent to roughly 0.51 lb/1000 lb of flue gas). The first comprehensive effort to restrict the emission of SO2 resulted from the passage of a 1937 law in St. Louis. This regulation stipulated that coal containing in excess of 23% volatile matter and 2% sulfur must be washed, thereby presumably producing some effective reduction in the input sulfur content. This was followed in 1949 by a Los Angeles County law which prohibited the emission of SO2 in concentrations greater than 0.2%. Most SO2-restrictive legislation passed since that date has been based on this limiting 0.2% SO2 by volume, although modifications are occasionally permitted under selected conditions, sometimes based on the fact that certain limiting ground concentrations are not exceeded — such as in the rules adopted by the San Francisco Bay area. To date, no legislation has been passed in the U.S. to limit the generation of nitrogen oxides from the combustion of fossil fuels. However, such oxides are considered to be of potential importance in air pollution control because of their possible detrimental effects on health and their reported role in the formation of photochemical smog. Interest in reducing oxides of nitrogen from powerplant and auto exhausts is increasing and regulations limiting their quantity can be expected in the future.

Jan 1, 1968

By AIME AIME

THE report of the united. States Steel Corporation for the' year 1928 gives the, following ,figures of raw materials and' finished products . Raw materials, tons :

Jan 1, 1929

By J. L. Kenty, J. P. Hirth

The concept of a critical super saturation, below which the nucleation rate is essentially zero and above which it is essentially infinite, is discussed with reference to vapor-solid nucleation. The necessary and sufficient conditions deduced for observations of this type of behavior are: 1) the nucleation rate must exhibit a sharp dependence on super saturation, 2) the growth rate must be sufficiently large that nuclei become observable in the time period of the experiment, and 3) the number of highly preferred nucleation sites must be small. Experiments reveal that the nucleation of silver on sodium chloride is visually detectable at all experimentally accessible super saturations and does not exhibit critical nucleation behavior. Failure to observe a critical super saturation is attributed to the insensitivity of nucleation rate to supersaturation as a consequence of the particular values of the contact angle and the surface free energy for this system. THE concept of a critical supersaturation, below which the nucleation rate is essentially zero and above which it is essentially infinite, arises naturally in homogeneous nucleation theory. Experimentally this type of behavior has been found by Volmer1 and others for water and other low surface tension liquids, as reviewed by several authors.2'3 The same type of behavior has been predicted and observed for heterogeneous nucleation of solids by Yang et al.4 and others,596 as also recently reviewed.2,7,8 In the work reported here on the heterogeneous nucleation of silver on NaC1, however, no critical super-saturation was found. Similar observations have been made recently for other systems.9-11 These results led to a reexamination of nucleation theory which revealed that there are conditions for which critical behavior is not predicted, either for homogeneous or heterogeneous nucleation. Although heterogeneous nucleation is of primary importance in this paper, some insight into critical behavior for such a case can be gained by considering homogeneous nucleation. Accordingly both types of nucleation theory are reviewed briefly. The requisite conditions for critical supersaturation behavior are then considered. The experimental results for the nucleation of silver on NaCl are presented and interpreted in terms of the theoretical presentation. REVIEW OF NUCLEATION THEORY There are essentially two approaches to nucleation theory, the so-called classical theory involving the concepts of bulk thermodynamics, and the statistical mechanical theory in which nuclei are regarded as macromolecules. The classical theory is based on the work of Volmer and Weber12,13 and Becker and. Doring14 and has been extended by Pound et al.15 The crucial assumption in the classical theory is that the small clusters or nuclei can be characterized by the same thermodynamic properties as those of the stable bulk phase. Thus, the nuclei are assumed to have a surface free energy, y, and a volume free energy of formation (relative to the vapor phase), ,, identical to that of the bulk. For deposition under low super-saturation conditions, the nuclei are large and this assumption is satisfactory. However, in many cases of interest, the nuclei contain only a few atoms and this assumption is highly questionable. The statistical mechanical models originated, for the specific case of a dimer as the critical nucleus, with the work of Frenkel16 and were extended later to larger sizes by Walton,17,18 Hirth19 and, more recently, Ht Zinsmeister. These models describe the nucleus in terms of a partition function, the estimation of which is tractable for clusters of 2 to 10 atoms, but extremely difficult for clusters larger than 10 atoms. Although the classical and statistical mechanical models are expected to apply for the limiting cases of large and small nuclei, both are uncertain for intermediate sizes. In this paper we shall treat only the classical model, recognizing that it is exact only for large nucleus sizes and regarding it as a phenom-enological description for small nucleus sizes. When analyses of experimental data using bulk properties show the nucleus size to be small, the resulting parameters should be regarded as largely empirical parameters describing the relative nucleation potency of the system. Considerable justification for the continued use of classical theory is provided by its general success in predicting nucleation behavior as a function of supersaturation and temperature. We emphasize that the qualitative features of the statistical mechanical models, particularly the critical super-saturation behavior that is central to the present work, are the same as those of the classical model. Of course, potential energy terms and surface partition functions replace the volume and surface energy terms of the latter model. The most recent versions of classical nucleation theory have been extensively reviewed.2,3,7 so that only the results are presented here. For homogeneous nucleation of a condensed phase from the vapor phase, the volume free energy change is ?Gv=vrT = =^ln£ [1] where v is the molecular volume of the condensing species. The supersaturation ratio,

Jan 1, 1970

By A. C. Fraker, H. H. Stadelmaier

WIENER and Bergerl reported the existence of the nitrides Fe3NiN and Fe3PtNwith a cubic L1'2 structure. The present note shows that a similar nitride Fe3PdN can be observed and that the composition range between the iron nitride Fe4N and the nitrides Fe3NiN, Fe3PdN, and Fe3PtN is occupied by single-phase cubic nitrides with structures intermediate between L1' and L1'2. The materials used in this investigation were electrolytic iron of 99.9 pct purity, carbonyl nickel of 99.7 pct purity, sponge platinum of 99.95 pct purity, and palladium sheet of 99.8 pct. purity. Binary alloys of the transition metals were induction-melted in a crucible of fused alumina, powdered, and screened to a particle size of - 200 mesh. The powders were nitrided at 600°C in a gas mixture of ammonia and hydrogen, and the crystal structure was determined with the aid of a Wilson powder camera. The results are compiled in Table I together with information from the paper of Wiener and Berger.1 The compound at the nominal composition Fe3PdN has a diffraction pattern with prominent reflections of a face-centered cubic lattice (h2 + k2+l2 = 3, 4, 8, 11, 12, 16) and weaker superstructure lines (h2 + k2 + 12 = 1, 2, 5, 6, 9, 10, 13, 14). With decreasing palladium content the superstructure lines become weaker and approach the intensity of those of Fe4N. No analysis was made of the intensities, but it can be assumed that the structure is that found by Wiener and Bergerl in Fe3NiN and Fe3PtN, namely L1'2 (perovskite structure) with both palladium and the interstitial nitrogen fully ordered. The dependence of the lattice constant upon the solute atom (Ni, Pd, Pt) content can be explained tolerably well by simple lattice expansion due to subsequent work confirms this suggestion, it will be of significance to order-disorder theory. The author is grateful to Lester Guttman for discussions on this topic.

Jan 1, 1961

By R. A. Burmeister, G. P. Pighini, P. E. Greene

An open tube vapor phase epitaxial growth system has been used for large area (multiple substrate) growth of GaAs1-xPx on GaAs substrates. The GaCl-GaCl transport reaction is used with either a GaAs or Ga (nonsaturated) source. Selenium and tellurium have been used for donor impurities, and zinc as an acceptor. The useable substrate area in this system is approximately 20 sq cm. The uniformity of thick-ness of the epitaxial layers are typically better than ±5 pct across a given wafer. Electrical and optical measurerments indicute comparable uniformity in electrical and luminescent properties within a wufer. The application of this system to the large scale pro-duction of GaAs1-x Px for display devices, both discrete and arrays, is discussed. Typical electrical and luminescent properties of light emitting diodes fabricated front material produced by this technique are presented. THE most promising materials currently being utilized for visible injection electroluminescence are GaAs1-xPx, Ga1-xAlxAs, and Gap. All have reasonably efficient emissions in the red portion of the visible spectrum at room temperature; Gap also has an efficient green emission.' At present, GaAs1-xPx has a technological advantage over Ga1-xAlxAs and Gap for display applications, since relatively large (several sq cm) areas of GaAs1-xPx suitable for use in electroluminescent devices may be readily grown by vapor phase growth techniques. In contrast, the preparation of Gap and Ga1-xAlxAs for electroluminescent device applications generally employs solution growth techniques which are at present not well suited for the growth of large areas of uniform thickness and doping level. The capability of uniform growth over large substrate areas and the use of multiple substrates is necessary for the practical utilization of electroluminescent devices. This is particularly important when quantity production or monolithic devices are required. Furthermore, in many display applications arrays of light emitting devices are used, the individual elements of which are of a size resolvable by the unaided eye. Thus the overall dimensions of display are substantially larger than those of most semiconductor devices. It is also necessary to achieve a high degree of control over the growth parameters to attain the required degree of reproducibility of materials properties for electroluminescent devices. In the case of GaAs1-xPx it is necessary to accurately and precisely control the phosphorus content of the alloy, both on a macroscopic and microscopic scale, in addition to the parameters generally associated with epitaxial growth such as thickness and doping level. This value is critical, as it has a major effect on the performance of electroluminescent devices. This paper describes the epitaxial growth of GaAsl-xPx suitable for electroluminescent display devices using a system developed specifically for this purpose, and which contains several novel features. The results of studies of selected physical properties of the epitaxial layers are also discussed. Finally, a brief summary is given of the characteristics of display devices fabricated from GaAsl-xPx grown in this system. EXPERIMENTAL A) Reactants. A number of techniques suitable for the vapor phase epitaxial growth of GaAs1-xPx have been reported in the literature.'-' The method selected for this investigation is that in which the Ga is transported by the GaC1-GaCI3 reaction in an open tube process. The results reported here were obtained using either the combination of GaAs, AsC13, and pH3, or Ga, AsH3, pH3, and HC1 as the initial re-actants.* The ASH3 and pH3 were obtained as dilute *Several different sources of supply were used for these reactants, y~elding comparable results._____________________________________________________ mixtures in HZ; the HC1 was obtained from the reduction of AsC13 by Hz at elevated temperatures. Both selenium and tellurium were employed as donor impurities, and zinc as an acceptor impurity. Selenium was introduced in the form of H2Se, tellurium in the form of tellurium-doped GaAs, and zinc in the form of diethy1 zinc. B) Apparatus. The prinicipal difference between the apparatus used in the present study and that of Tietjen and Amick,8 in addition to size and other related design features, is that RE induction heating is utilized in place of resistance heated furnaces. Induction heating was selected for this application because it appears to have several advantages, including: 1) It is possible to keep all fused silica portions of the apparatus at temperatures well below those of the reaction zone, thus minimizing a possible source of contamination. 2) The thermal mass of an induction heated system can be made small, thus reducing the total time required for the growth process. 3) Sharp temperature profiles (desirable for high deposition efficiency) are easily achieved. 4) The volume of the system for a given substrate area can generally be made smaller than a comparable resistance heated unit. This results in shorter time

Jan 1, 1970

By H. H. Otto

Fourteen years ago, J. B. Warriner presented before the Institute a paper on anthracite stripping,' describing the progress of stripping in the Anthracite Region from its beginning with an old quarry stripping at Summit Hill, which was operated more than a century ago, through various types of strippings used in 1917. This paper will briefly review the status of anthracite stripping methods from 1917 to the present day and describe in detail the stripping operation of The Hudson Coal CO. at Clinton collicry. It is not intended as a review of the work in the district—that would require a much longer paper. History and Statistics Mr. Warriner said, in part: "The sizes of shovels have gradually increased until now 70 and 80-ton shovels are the rule and larger equipment is coming in." He also referred to a large electrically operated dragline which weighed about 225 tons and had an operating radius of 125 ft. In 1917, a number of strippings used shovels of various sizes, ranging up to the 60 Marion and Bucyrus 70-C railroad type. Material was hauled away in narrow-gage side dumpers, usually of 4 or 5 cu. yd. capacities. Star-type churn drills with 4-in. bits were generally used for drilling purposes. Since 1917 wages in the anthracite field; have increased, but the higher operating costs of strippings are now being successfully combated by continuous improvements in stripping equipment, such as the development of the caterpillar or crawler shovels, the use of larger cars, better drilling equipment, the introduction of shovels of increased capacity and the adoption, in a number of instances, of standard-gage equipment for transportation. In 1918 another large dragline was introduced in the southern fields, which had been in service in the Middle West and is in use today, dipping vertically about 180 ft. to raise coal out of a stripping. About 1918, small shovels with caterpillar traction were introduced. In 1922 the 6-in. well drills began replacing the 4-in. drills, with an attendant saving to the operators. About the same time A. E. Dick placed the first pair

Jan 1, 1931

By JAS. F. McCARTHY

THE present Hecla Co. is a Washington corporation; the Hecla Co. of Idaho was the old company. The older corporation owned two claims, the Hecla and the Katie May, and was incorporated for 500,000 shares of one dollar par value. The principal shareholders and officials of the older company were among the early mining men of the camp. Among the active officials were John A. Finch and A. B. Campbell. Among the directors and share- holders were Patrick Clark, J. R. Smith, Frank Upman, F. J, Kipp, Chas. Kipp, B. A. Kipp and Carl Landsee. F. J. Kipp and Carl Landsee are now directors of the Company. All of the others mentioned have died, but the surviving members of their families retain their ownership in the Company's shareholders. B. A. ,Kipp, who recently died, was the largest shareholder at the time of incorporation and Patrick Clark was the second largest shareholder. B. A. Kipp is a brother 'of F. J. Kipp, director of the Company.

Jan 1, 1924

By N. A. Zeigler, T. D. Yensen

Aging is a term that connotes a slow change in properties under ordinary operating conditions. It can be accelerated by increasing the temperature and by mechanical straining. The magnetic properties of iron and some of its alloys have for many years been known to be subject to such a change. But the cause of the change was not recognized until a few years ago after mechanical age-hardening in non-ferrous alloys of the "duralumin" type had been definitely shown, by means of solid solubility curves, changes in electrical resistance and microanalysis, to be caused by slow precipitation of one or more constituents from the solid solution. The similarity between the solid solubility curves of such alloys (Fig. 1) and those for iron-nitrogen (Fig. 2) and iron-carbon alloys (Fig. 3) below the A1 transformation point suggested at once that magnetic aging of iron might be caused by a similar process; namely, by the slow precipitation of carbon and nitrogen in the form of Fe4N and Fe3C at ordinary temperatures because of a cooling rate that had been too rapid to permit complete precipitation according to equilibrium conditions. This suggestion has since been amply confirmed, particularly by the comprehensive work of Köster1 on the effect of nitrogen and carbon. Typical curves are shown in Fig. 4 for the relationship between aging temperature and coercive force. Previous to the establishment of the precipitation-hardening theory it was thought that the effect of nonmetallic elements like C, N, O, etc., on the magnetic properties of iron was greatest when these elements were retained in solid solution, atomically dispersed throughout the interstitial spaces of the iron lattice2. Based on the theory that magnetic properties are intimately connected with the regularity of the lattice, it now follows quite logically that a greater effect on this regularity may be obtained when the above impurities are precipitated as very fine particles of Fe3C, Fe4N, FeO, etc., more or less uniformly dispersed within the grains. But if this is the case, it follows also that there must exist a relationship between the size

Jan 1, 1935