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By B. S. Butler

AN understanding of mineralizing solutions and how they carry and deposit metals is of prime importance to students of ore deposits. Lindgren states: "The whole problem surely is very complicated. One difficulty is that we know so little about the stability field of ore minerals."1 Lindgren further states: It is believed that they [the solutions] were in small part oxidized to sulphates, for instance, but in large part they were composed of hydrogen sulphide, alkaline sulphides and various halogen compounds. Doubtless, however, free carbon dioxide was present. Becker's view of the double sulphides as important constituents of the solutions probably holds good. In the fourth edition of Mineral Deposits2 Lindgren had changed his views somewhat: From the work of Day, Allen, Shepard, and others, it would seem probable that many of the volcanic gases are acid when given off but are in unstable equilibrium, and could not have preserved this acid character after having been long in contact with the surrounding rocks. It is believed that they were in small part oxidized to sulphates, for instance, but in larger part they were composed of hydrogen sulphides, alkaline sulphide, and various halogen compounds. Doubtless, however, free carbon dioxide was present. Becker's view of double alkaline sulphides as important constituents of the solution probably holds good. The writer wonders if progress would not result from an attack on the problem in steps, the steps to contribute to the attack on the whole. The initial step would deal with the simpler bodies of supposed magmatic (hydrothermal) origin, that is, those composed essentially of silicates, oxides, sulfates, and sulfides. The following discussion attempts to develop one step of a method that was proposed on a more comprehensive scale in 1929 by the writer and W. S. Burbank.3 The accompanying partial table (Table I) of the electromotive series is from a table distributed by Merck & Co. Inc., manufacturing chemists, prepared in turn from Fundamental Chemistry.& The electromotive arrangement brings together elements that in hypogene ore deposits occur: 1) in oxygen combination only; 2) in combination with sulfur as well as with oxygen; and 3) as sulfides, arsenides etc., and as native metals, see Table 11. The writer clearly recognizes that he is not qualified to discuss the formation of ore deposits as a chemical problem, but he feel that some of the relations that are met by the geologist can well be stated with the hope that the chemical explanation will be forthcoming. By consideration of a group including mainly the elements oxygen, hydrogen, sulfur and iron, complications are avoided, especially with elements of the lower electromotive group. The results can only contribute to the solution of the problem, not to the completion of it. The pH and Eh of the solutions and also temperature probably determine what minerals form. The mineral groups that contain elements high in the electromotive series are alumino-silicates, titanites, simple silicates, spinels, oxides, carbonates and sulfates, in all of which the elements are combined with oxygen. These groups are also recognized as the general order of temperature at which the minerals start to form, see Table 11. At low temperature are sulfides, arsenides, antimonides, sulfo-salts, and native metals, in all of which the elements are characteristically not combined with oxygen. The intermediate temperature group contains elements that form both oxygen compounds and sulfur compounds.

Jan 1, 1957

R,. P. JaRvis,* El Oro, Estado de México, México.—The practical problem raised by Mr. Wisser—that is, the determination of the lower limit of ore deposition, below which it is useless to look for ore shoots—is one of the most important in economic geology. He asks: "Can we learn to determine the position of such a line?" For individual districts, yes; but its determination has always been by empirical methods; that is by actually exploring the veins to such depths that the values drop below the economic limits. Usually the signs are plain enough that values have been bottomed without confirmation by the chemist or assayer. Most veins, when approaching their limit, begin to split into branches or stringers; the vein matter itself undergoes a change from "lively looking" rock to one that is dull and unpromising, the quartz, instead of having segregated into clean vein matter, has simply spread itself into the country rock, rendering this more siliceous but no richer—these, together with inclusions of the country rock in the vein, are all positive indications of the limit. Mr. Wisser seems disposed not to accept the law of cause and effect, which he calls "empiricism." He says: "Empiricism embodies an assumption perhaps not evident at first glance. It is this: that like effects spring from like causes and therefore necessarily have a common meaning." There can be no doubt as to the validity of this law, since it is the foundation stone upon which are built all inductive sciences, including economic geology. When demonstrable, proved facts become confused with inferences, as they seem to be generally in the paper under examination, no sound conclusions can be reached. Mr. Wisser has failed to give sufficient data covering the two vein systems which he cites as examples. Presumably they are situated in the Pachuca District of Mexico, but not everybody is familiar with the vein systems there in spite of the fact that it is world famous as a silver producer. Are these two systems separated some distance horizontally from one another and how far? He has given no estimate of the amount and kind of rock that has been eroded from over the present veins. His description of the two systems appears on page 100, beginning: "1. East-west veins," and ends on page 101, "they would lack spaces there in which to deposit." On page 101, with the paragraph beginning "On the other hand," he gives a picture of what he believes takes place in class 2 veins. The sum of this seems to be, according to Mr. Wisser's observations, that, in the east-west veins, class 1, there has been an invasion of an "altering solution," which I judge has been responsible for the formation of extensive "alteration haloes"; that these alteration solutions have followed along pre-existing fractures or fissures; and that after these alteration solutions finished their work the mineralizing solutions deposited the vein matter and metallic values. Mr. Wisser does not specify clearly what the "alteration haloes" consist of; in other words, what change the original rock has suffered, whether oxidizing, carbonating, or sulphidizing. If they came from depth they could not be oxidizing or carbonating, and in this case it is a bit

Jan 1, 1941

R,. P. JaRvis,* El Oro, Estado de México, México.—The practical problem raised by Mr. Wisser—that is, the determination of the lower limit of ore deposition, below which it is useless to look for ore shoots—is one of the most important in economic geology. He asks: "Can we learn to determine the position of such a line?" For individual districts, yes; but its determination has always been by empirical methods; that is by actually exploring the veins to such depths that the values drop below the economic limits. Usually the signs are plain enough that values have been bottomed without confirmation by the chemist or assayer. Most veins, when approaching their limit, begin to split into branches or stringers; the vein matter itself undergoes a change from "lively looking" rock to one that is dull and unpromising, the quartz, instead of having segregated into clean vein matter, has simply spread itself into the country rock, rendering this more siliceous but no richer—these, together with inclusions of the country rock in the vein, are all positive indications of the limit. Mr. Wisser seems disposed not to accept the law of cause and effect, which he calls "empiricism." He says: "Empiricism embodies an assumption perhaps not evident at first glance. It is this: that like effects spring from like causes and therefore necessarily have a common meaning." There can be no doubt as to the validity of this law, since it is the foundation stone upon which are built all inductive sciences, including economic geology. When demonstrable, proved facts become confused with inferences, as they seem to be generally in the paper under examination, no sound conclusions can be reached. Mr. Wisser has failed to give sufficient data covering the two vein systems which he cites as examples. Presumably they are situated in the Pachuca District of Mexico, but not everybody is familiar with the vein systems there in spite of the fact that it is world famous as a silver producer. Are these two systems separated some distance horizontally from one another and how far? He has given no estimate of the amount and kind of rock that has been eroded from over the present veins. His description of the two systems appears on page 100, beginning: "1. East-west veins," and ends on page 101, "they would lack spaces there in which to deposit." On page 101, with the paragraph beginning "On the other hand," he gives a picture of what he believes takes place in class 2 veins. The sum of this seems to be, according to Mr. Wisser's observations, that, in the east-west veins, class 1, there has been an invasion of an "altering solution," which I judge has been responsible for the formation of extensive "alteration haloes"; that these alteration solutions have followed along pre-existing fractures or fissures; and that after these alteration solutions finished their work the mineralizing solutions deposited the vein matter and metallic values. Mr. Wisser does not specify clearly what the "alteration haloes" consist of; in other words, what change the original rock has suffered, whether oxidizing, carbonating, or sulphidizing. If they came from depth they could not be oxidizing or carbonating, and in this case it is a bit

Jan 1, 1941

By S. S. Shen, M. J. Pool, P. J. Spencer, J. R. Guadagno

VERY few thermodynamic data are available for rare-earth alloys, partly because of the difficulties of obtaining the metals in sufficiently pure form and also because of their comparative scarcity up to the present time. The rare earths form a very interesting series in the periodic table in view of the progressive filling of their 4f subvalence electron shell and would be expected to provide useful information with regard to alloying characteristics of transition elements. It has been found in recent calorimetric investigations that the heats of solution of a number of the rare-earth metals in liquid tin are highly exothermic.1-4 Exceptionally strong bonding between rare-earth and tin atoms is clearly indicated in the liquid solutions. Continued thermodynamic studies of the behavior of rare earths in solution could thus contribute a great deal to present theoretical knowledge of alloying behavior and would yield an insight into bonding of a strength hitherto unencountered in liquid alloys. The determination of the heats of solution of the pure components in liquid tin is an essential preliminary to calorimetric work of this nature. Heats of solution of praseodymium, neodymium, and samarium in liquid tin at 750" ' and the heats of mixing of Pr-Nd solid solutions' have already been determined in this laboratory. The present investigations with lanthanum continue the study of rare-earth elements. Details of the construction and operation of the liquid metal solution calorimeter used in this work have been published previously by Pool and Peluso and no further description will be given here. The lanthanum used in heat of solution determinations was supplied by Lunex who quoted the purity as 99.9 pct. Their detailed analysis of the material is given in Table I. Samples of 0.0003 to 0.0005 g-atom were used for each run and great care was taken to remove all surface oxide prior to weighing. The samples were stored at all other times in a beaker of oil to prevent their otherwise rapid oxidation. The compounds LaSn (Cudu, L1P type structure) and La&, (structure not classified) were prepared from the appropriate quantities of the two pure components by arc melting under a purified argon atmosphere and once again great precautions were taken to avoid any subsequent oxidation of the specimens. Although no structural examination of the compounds was made, the consistency of thermodynarnic measurements carried out on twenty or so individual samples of each indicates that the compounds were in fact homogeneous, single phase alloys. Samples of the compounds consisting of 0.0003 to 0.002 moles were used in the calorimetric measurements. A solvent bath consisting of approximately 80 g of 99.9 pct pure Sn was used for each series of runs and its heat capacity was determined at regular intervals throughout the experiments using pure tin or tungsten calibration samples. Measurements were made of the heat of solution of lanthanum in liquid tin at 725", 750C, and 775°K and at compositions up to 2.21, 4.76, and 5.25 at. pct La at the three temperatures respectively. In every case, the heat of solution of lanthanum remained constant at its limiting value, within experimental limits, up to the highest lanthanum concentration investigated. Since no change in was observed, it was concluded that the liquid/liquid + LaSn, phase boundary had not been

Jan 1, 1969

By Mark J. Klein, Robert A. Haggins

The pesence of a small amount of oxygen was found to cause significant grain growth restraint in 99.99 pct Ag. This behavior does not seem to be due to the presence of an oxide dispersion, but instead, to be related to the existence of minute amounts of oxygen m solid solution. In the amounts necessary to cause the observed effects it was found that oxygen migrates with extreme rapidity, probably along extended structural imperfections, such as dislocations and grain boundaries. A number of years ago, hastton' observed that the presence of small amounts of oxygen caused a retardation of grain growth in silver. He attributed this behavior to the formation of a fine dispersion of oxide particles by the internal oxidation of trace impurities. More recently, wood2 also found that oxygen caused grain growth restraint in copper. Experiments using both copper and a dilute solution of aluminum in copper led to the conclusion that the effects observed in copper were due to oxygen in solid solution, rather than an oxide dispersion. During the course of a study of the influence of several solutes on the recrystallization of Silver, the presence of minute amounts of oxygen was found to exert a very significant influence on grain growth. The experiments reported here were undertaken to determine whether the grain growth restraint observed in silver due to the presence of oxygen is related to oxygen in solution or to an oxide dispersion. Because of the difficulty in measurement and control of the very small oxygen concentrations causing the observed effects no attempt was made to treat the data in a quantitative manner. EXPERIMENTAL PROCEDURE AND RESULTS Silver of 99.99 pct purity was melted and cast into slabs in a vacuum of better than 0.1 p. These slabs were reduced 50 pct by cold rolling to a thickness of approximately 2.5 mm. Samples cut from this material were annealed in vacuum for a series of different times at 803°C. Another group of samples was similarly annealed in air. This temperature is well above the recrystallization range for silver of this purity (150" to 200°C). The mean grain diameter of these samples was measured, both in the center and near the edge, using the line-intel-cept method, and is shown as a function of annealing time in Fig. 1. The grain size in the centers of the samples annealed in air was found to be larger than that of the surface regions, while the grain growth behavior of the edge and center regions annealed in a vacuum was approximately the same. he edge measurements were taken at a distance of 0.2 mm from the surface.) A few samples were annealed in nitrogen. Their behavior was identical to that of the vacuum-annealed samples. Samples annealed in oxygen had approximately the same grain growth behavior as those annealed in air, leading to the conclusion that this behaviouer is due to oxygen. The microstructure of a sample annealed in air at 803" for. 30 minutes is shown in Fig. 2. The smaller grain size near the surface is characteristic of the iir-annealed specimens. Possible causes of this grain growth restraint in the air-annealed specimen are the formation of an im-

Jan 1, 1962

By B. F. Tillson

There is a dearth of information on the economic threat of silicosis. Even the insurance companies and rating bureaus are in a quandary, and the majority of them avoid any action that will stir up an awakened public consciousness of the serious nature of this industrial hazard. Individual claims for $100,000 are now common in silicosis lawsuits. Because of ('hidden costs," in lowered plant efficiency, the total cost of this disease to industry is probably four times its apparent direct cost. The direct costs vary with the labor policies of the employer and with the labor legislation in force. Direct costs may originate in three ways: (1) voluntary assumption by the employer of medical expenses and loss of earning power of stricken employees; (2) state enforcement of industrial disease compensation acts; and (3) awards or settlements after suits in common law. Examples are offered in the last two classifications. In the Rand, South Africa, compensation laws are in effect and in approximately 20 years prior to 1932 about $65,000,000 has been awarded for silicosis and an additional liability of $34,000,000 incurred, or an average of about t5,000,000 per year. During 1932 silicosis compensation on the Rand was about $6,000,000. No figures are available for the direct capital or operating costs for preventive measures there, nor for the additional "hidden costs." It might be reasonable to assume that silicosis has cost the gold-mining industry of South Africa twenty to twenty-five millions of dollars per year. It is estimated that common-law silicosis claims have, in the last few years, aggregated $50,000,000 in New York State alone and have exceeded $300,000,000 in the United States. Attention is called to the involved nature of the insurance situation for industrial diseases in contrast to accidents. The indeterminant, insidious nature of silicosis makes it particularly difficult to predict necessary insurance premiums and reserves. The serious hazard of this disease was not properly appreciated by either insurance companies or industrialists, so sufficient study has not been given its causation, prevention, detection, treatment, and compensation. Therefore legal difficul-

Jan 1, 1934

By AIME AIME

THE organization of the Board of Directors was effected Tuesday afternoon in ' executive session. Messrs. Bassett,. Buehler, Cates, Daveler, Eavenson, Eilers, Elliott, Evans, Guess, Lovejoy, Moulton, Rickard, Tally, Turner,, Wraith and Wright being pres¬ent. Messrs. Tally, Bassett, Rickard, Mathews and Cates were chosen to form the Executive Committe with Mr. Tally as Chairman, and Messrs. Krumb, Guess and Moulton for the Finance Committee with Mr. Krumb as chairman. Karl Eilers was reelected as Treasurer and H. Foster Bain as Secretary, after which the Directors adjourned for the usual dinner reported elsewhere. At the open session of the Board, at which in addition Messrs. Allen and McAuliffe were present, the work of organization was continued with appointments to committees as listed herewith. Various actions of the Executive and Finance Committees were confirmed, the budget for 1931 formally approved, the meeting dates for the year adopted, 34 new Members and Associates, 13 Junior Members and 31 Student Associates admitted by election and transfer and 29 resignations accepted.

Jan 1, 1931

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Jan 1, 1928

By Asheim, Harald A.

Parameter estimates affect both the optimum field development decisions and the economic result. A general methodology for assessment of the effects of parameter uncertainty in offshore development decision situations is proposed, and used to analyze aspects of the initial development situation for the Statfjord field.

Jan 1, 1982

By L. V. Gregor, C. F. Aliotta, P. Balk

The structure of silicon surfaces, thermally oxi&zed in dry oxygen and in steam, was studied using the electron microscope. It was found that the structure on the original (etched) surface is retained at the outer surface of the oxide, whereas the oxide-silicon interface is smoothed out considerably. This supports the idea that, both in oxygen and in steam, the oxidation reaction occurs at the oxide-silicon interface. Mechanical damage of the original silicon surface affects the rate of oxidation. It also changes the chemical properties of the oxide, as shown by the enhanced rate of etching in buffered HF at the locations of damage. However, the oxide at the originally damaged surfaces still exhibits a high electrical breakdown strength. Exposure of thermal oxides to P205 or BzOs vapor, which will yieldphospho- or borosilicate layers, results in complete annihilation of all fine structure on the surface. Reaction of silicon with C02 gives a surface film which probably does not consist of pure SiO,. THERMAL oxidation of silicon yields uniform and strongly adhering oxide films which are normally amorphous and continuous. Contamination and surface imperfections have been reported to cause local crystallization and the formation of pinholes."' The parabolic-rate law of film growth observed by several workers for the oxidation both in steam and in dry oxygen at higher temperatures suggests that diffusion of one or more reactants through the oxide is the rate-deter mining step. One of the dif-fusants is an oxygen species and oxide is continuously formed at the oxide-silicon interface. This was concluded for high-pressure steam oxidation by Ligenza and spitzer5 from an infrared-absorption study of the isotopic exchange of oxygen. Jorgensen arrived at the same conclusion for the oxidation in dry oxygen by measuring during oxidation the resistance change between silicon and a porous platinum marker electrode in the oxide. Recently, Pliskin and Gnall' reported similar conclusions concerning the growth mechanism from controlled etch studies using a phosphosilicate marker. The work communicated in the present paper was aimed at studying oxide growth on locally damaged silicon substrates and relating it to the chemical behavior and electrical breakdown properties of the films. Since etched and oxidized silicon surfaces normally appear to be very smooth when examined by optical microscopy except for some occasional pits, it was decided to use the electron microscope as a tool. In this way, the detection of surface roughness and damage on a scale comparable to or smaller than the thickness of the film is possible. Also, the microstructure of the original substrate surface constitutes a built-in marker which represents a minimum of perturbation to the growing oxide layer, and no foreign material is introduced. Thus information on surface reactions and additional evidence on the location of oxide formation in steam and in oxygen could be obtained. EXPERIMENTAL Electron micrographs7 were obtained using a Philips EM100 electron microscope. Collodion surface replication was used since this is a nondestructive technique and thus permits replicating the same surface at different stages of processing. In order to establish the effect of different treatments it was found essential to make successive observations of the same area by using a reference point. Reference points were conveniently provided by scribing a small v mark on the original surface with a silicon carbide tip. This procedure yields damaged and damage-free areas near the reference point. Upon replication, the samples were thoroughly cleaned before subjecting them to the next process step. Mechanically lapped silicon wafers (Dow-Corning, 100 ohm-cm p-type, cut perpendicular to the (111) direction) were chemically polished in a rotating beaker with a mixture of 1 part HF (48 pct), 2 parts glacial acetic acid, and 3 parts HNO3 (70 pct) by volume. This procedure yields a smooth surface with a faint "orange peel'' structure due to a "ripple" less than 20002i deep. Oxidation in steam or oxygen was carried out in an Electroglas tube furnace. Steam oxidations were always preceded and followed by a brief exposure to oxygen at the same temperattre. The thicknesses of the oxide films under 3000A were determined with a Rudolph Model 436-2003 ellipsometer,' whereas those over 3000A were measured using the VAMFO technique. In the present study, a solution of 300 g of N&F in 25 ml HF (48 pct) and 450 ml water was used to detect areas of increased chemical reactivity in the

Jan 1, 1965

For the year ending February, 1918 PRESIDENT PHILIP N. MOORE ST. Louis, Mo. PAST PRESIDENTS WILLIAM L. SAUNDERS NEW YORK, N. Y. L. D. RICKETTS, NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY J. JENNINGS, NEW YORK, N. Y. TREASURER GEORGE C. STONE, NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND,.. NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 3, 1917

Executive-A. R. LEDOUX, chairman. Membership-J. V. W. REYNDERS, chairman. Finance-J. V. N. Dorr, chairman. Library-E. GYBBON SPILSBURY, chairman. Papers and Publications-BRADLEY STOUGHTON, chairman. Nominations-POPE YEATMAN, chairman.

Jan 12, 1919

The Institute has no available copies of Bulletin No. 7, January, 1906, and Bulletin No. 105, September, 191.5. The sum of 30.50 per copy will be paid for these Bulletins.

Jan 6, 1917

IRON AND STEEL COMMITTEE ALBERT SAUVEUR, Chairman. A. A. STEVENSON, Vice-Chairman. HERBERT M. BOYLSTON, Secretary, Abbot Bldg., Cambridge, Mass. John Birkinbine, William Kelly, J. S. Unger, William H. Blauvelt, Charles Kirchhoff, Felix A. Vogel, James Gayley, Richard Moldenke, Leonard Waldo, Henry D. Hibbard, Joseph W. Richards, William R. Walker, Henry M. Howe, C. F. W. Rys, William R. Webster, Robert W. Hunt, E. Gybbon Spilsbury, Frederick W. Wood. J. E. Johnson, Jr.,

Jan 1, 1914

By E. C. Pechin

AT the suggestion of some members of the Institute, attention is called to the record of the working of Dunbar Furnace during the twelve months ending in January, 1874. During this period, with a product of over eleven thousand gross tons, not a single ton of

Jan 1, 1874