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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

By AIME AIME

MINING men in general- are a roving lot but not so Selwyn G. Blaylock. Immediately after graduation from McGill in 1899 he went to the Trail smelter and he is there today though he spent three or four years of his early professional life at other British Columbia mining centers. Either he sensed the great possibilities of the company of which he is now vice-president and general manager, or it sensed his; more probably both. Certainly the association was a happy and fortunate one.

Jan 1, 1937

By U. C. Tainton

IN reviewing progress in zinc metallurgy during the last year or so one is reminded of the premise on which H. G. Wells based his "Food. of the Gods," namely that growth does not and cannot take place smoothly and steadily, but occurs in a series of bursts and intermissions: "It is as if every living thing has to accumulate force to grow, grows with vigor only for a time, and then has to wait for a space before it can go on growing again."

Jan 1, 1937

By Edward H. Robie

PONCA CITY proved an ideal selection as a place of meeting for the Petroleum Division this fall. The accommodations at the Conoco Club were just what was required for such a gathering; the committee having the arrangements in charge functioned with the efficiency of veterans and the enthusiasm of neophytes; and the members and guests followed the speakers with close attention, entered the subsequent discussions with gusto, and divulged the "low-down" at private conferences. No one minded the drizzling rain on the first day, which only served to keep up the attendance in the auditorium; the weather then cleared up in time for a group picture before the gathering went their separate ways.

Jan 1, 1932

By P. F. MINISTER

AT Lime Spur, Mont., the East Butte Copper Mining Co. has been quarrying limestone for twenty years. The quarry is beside the Northern Pacific R. R. in the Jefferson River canyon, 4 ½ miles east of Cardwell, at Lime Spur, Montana. HISTORY This quarry was opened early in 1900 by Dan Morrison of Whitehall, the discoverer of the Morrison cave, to supply a demand for smelter flux. Limestone was sold to the Pittsmont smelter of The East Butte Copper Mining Co. and to the Butte Reduction Works. As no particular effort was made at the quarry to select the rock that delivered to the smelters was unduly high in magnesia and impurities. The East Butte com¬pany, therefore. Bought the quarry. in 1909 and confined operations to the high-grade beds in order to supply rock of the desired purity for its own smelter and the Butte Reduction Works until the latter shut down. It also developed a market for some of its rock with the sugar factories. The latter market increased until in later years all rock, larger than 4 in. in size over a bar grizzly, was being shipped to the sugar factories, and the rock smaller than 4 in. was being used as a flux in the blast furnaces at the Pittsmont smelter. In 1924, the East Butte concluded a contract with the Anaconda company for the treatment of its ores, and the Pittsmont -smelter -was shut down: which made the minus 4-in. rock a useless by-product. Since there was not enough revenue in the sugar rock alone and also because of limited waste room it became necessary, if Lime Spur was to continue to operate, to increase- the proportion of plus 4-in. rock and to develop a market for the minus 4-in.

Jan 1, 1930

By M. H. Cullender

The performance characteristics 01 gas wells producing from formations which fail to stabilize within a relatively short period of time are obscured by the interrelation of the coefficient (C) and the slope "n" of the conventional back-pressure curve q = C(P2 f- p2s)n An empirical method is presented whereby the characteristic or true slope (11) of the back-pressure curve may be determined for a particular gas well. For those gas wells which do not stabilize within a relatively short period of time, the coefficient (C) is considered as a variable with respect to time and as a constant only with respect to a specific time. Thus, the back-presrure performance of such a well is presented as a series of parallel curve5, each curve representing the performance of the well at the end of a given time interval. Through use of the method presented, a simple presture gradient is developed and maintained within the drainage area around a producing gas well during the test period in order that the variation of the coefficient (C) with respect to time does not obscure the true value of the lope. INTRODUCTION The back-pressure method of testing gas wells as set forth by Schellhardt and Rawlins1 is dependent upon the requirement that a series of flow rates and corresponding pressure data be obtained under stabilized conditions. These data arc then plotted on logarithmic coordinates of flow rate (Q) vs difference in squared pressures (P2f — P2s) in order to determine the constants (C) and (n) for Equation 1. With respect to this method of presenting the performance characteristics of a gas well, it should be pointed out that although Equation 1 is an empirical relationship, the form of the equation was justified to a considerable extent by an independent development by Muskat and Botset.2 This development was theoretical in nature; however, certain assumptions with respect to the type of flow existing (viscous vs non-viscous) were madc which may or may not be correct. As the use of the method presented by Schellhardt and Rawlins spread through the industry, it became evident that the method of testing was applicable for those wells which approached stabilized prbducing conditions within a relatively short period of time. Performance characteristics could not be determined by this method, however, for wells which approached stabilized protlucing conditions slowly over a considerable period of time. This characteristic of "slow stabilization" has generally been associated with gas wells producing frorn reservoirs of low permeability. As the demand for natural gas continued to grow through the years, a great number of wells were completed in reservoirs of low permeability which exhibited "slow stabiliz:~tion" characteristics. Consequently, the problem of determining the true performancc characteristics of these wells became more apparent. It is with this problem in mind that the isochronal performance method of determining the flow characteristics of gas wells is presented.

Jan 1, 1956

By J. Jolly

THIS short note on the probable character of the organic sulfur compounds in coal can do no more than indicate lines of research. We have no new experimental work to describe, nothing comparable in value with the careful studies of American coals by Powell and Parr1 and Yancey and Frazer.2 A study of the manner in which sulfur compounds exist in British coals (and their behavior on heat treatment) is rendered increasingly necessary by the fact that the British reserves of good coking coals of reasonably low sulfur content are fast being depleted. We believe that it is essentially by a study of the modes of formation, occurrence, and decomposition of the various types of inorganic and organic sulfur compounds in coal that it will be possible, with hope of success, to attack the problem of purifying coals, otherwise eminently suitable for coking, from these objectionable ingredients. Sulfur, so far as is at present known, does not normally occur in the free state in the coal conglomerate, but is chiefly distributed, irregularly, in three forms: 1. As primary constituents of the coal conglomerate, organic in nature and probably associated with those molecular complexes that have resulted from the degradation of the proteins of the plant tissues responsible for the formation of the coal mass. These constituents can be classed as "organic sulfur." 2. As metallic sulfides, e.g., iron pyrites. 3. As metallic sulfates, e.g., calcium sulfate and ferrous sulfate. (The occurrence of these compounds varies with the occurrence and degree of degradation of class 2.)

Jan 3, 1925

(Members are urged to send in for this column any notes of interest concerning themselves or their fellow-members) The following is a partial list of members and guests who called at Institute headquarters during the period May 10,1917, to June 10, 1917. F. J. Anderson, Cali, Colombia. W. F. Jahn, Kirkland Lake, Ont., Canada. George J. Bancroft, Denver, Colo. W. McA. Johnson, Hartford, Conn. W. F. B. Berger, Denver, Colo. J. E. Jopling, Marquette, Mich. F. J. Brulé, Toronto, Ont., Canada. William Kelley, Vulcan, Mich. J. Murray Clark, Toronto, Ont., Canada. H. M. LaFollette, La Follette, Tenn. Will L. Clark, Jerome, Ariz.. Dorsey A. Lyon, Washington, D. C. G. H. Clevenger, Palo Alto, Cal. James F. Magee, Lancaster, Pa. Paul S. Couldrey, Sound Beach, Conn. M. Ortin, Nijni-Novgorod, Russia. C. W. Crispell, Kingston, N. Y. - C. H. Palmer, Jr., Los Angeles, Cal. George A. Easley, La Paz, Bolivia. Edison S. Pettis, ?Mill Valley, Cal. Bancroft Gore, Butte, Mont. Mortimer A. Sears, Paintsville, Ky. John B. Guernsey, Roanoke, Va. W. J. Uren, Houghton, Mich. Rush M. Hess, St. Louis, Mo. C. E. Visel, New Haven, Conn. E. Hibbert, Nickelton, Ont., Canada. Percy E. Barbour, has resigned his position as managing editor of the Engineering & Mining Journal, to accept the appointment of Deputy Superintendent of the New York State Troopers, with headquarters at Albany, N. Y., with the rank of captain.. He has also been commissioned as captain in the 22nd Regiment, N: Y. N. G., having been formerly 1st Lieutenant.

Jan 7, 1917

By Henry Emmett Gross

Two types of decline curves are considered and their applications are discussed. The first is the well-known semilogarithmic decline curve having the rate of production plotted on the logarithmic scale and the time on the horizontal scale. The other curve is the percentage of oil in the fluid versus cumulative production, and it is plotted on Cartesian coordinate paper. These curves are illustrated by carefully and adequately labeled graphs. Where conditions permit application of both types of curves for rationally determining the reserves of a well, both should be applied and the most conservative reserve should be chosen. Formulas are given for determining the economic limits. For a semi-l~~arithmic~decline curve the formula is: A = B X C X D X E X F or B = A/C ? D X E X F A = total monthly operating cost (average of past year), B = economic limit in barrels of oil per day, C = days in an average month = 30.4, D = market price of crude per barrel, E = 1-royalty, F = 1-gross production tax, G = water production in barrels per day at the economic limit, H =per cent oil in fluid at economic limit. The economic limit for a per cent oil in the fluid curve is: H = B/B+G X 100 The semilogarithmic decline curve is treated first. Straight-line extrapolations on semilogarithmic paper follow the compound interest compound discount law, hence the ensuing formulas derived from this law may be used in computing reserves for such extrapolations: [1___1/(1+Y)]

Jan 1, 1939

By Henry Emmett Gross

Two types of decline curves are considered and their applications are discussed. The first is the well-known semilogarithmic decline curve having the rate of production plotted on the logarithmic scale and the time on the horizontal scale. The other curve is the percentage of oil in the fluid versus cumulative production, and it is plotted on Cartesian coordinate paper. These curves are illustrated by carefully and adequately labeled graphs. Where conditions permit application of both types of curves for rationally determining the reserves of a well, both should be applied and the most conservative reserve should be chosen. Formulas are given for determining the economic limits. For a semi-l~~arithmic~decline curve the formula is: A = B X C X D X E X F or B = A/C ? D X E X F A = total monthly operating cost (average of past year), B = economic limit in barrels of oil per day, C = days in an average month = 30.4, D = market price of crude per barrel, E = 1-royalty, F = 1-gross production tax, G = water production in barrels per day at the economic limit, H =per cent oil in fluid at economic limit. The economic limit for a per cent oil in the fluid curve is: H = B/B+G X 100 The semilogarithmic decline curve is treated first. Straight-line extrapolations on semilogarithmic paper follow the compound interest compound discount law, hence the ensuing formulas derived from this law may be used in computing reserves for such extrapolations: [1___1/(1+Y)]

Jan 1, 1939

By E. R. Parker, C. F. Riisness

That grain size has a great effect on the mechanical properties of metals has been recognized for a long time. Bassett and Davis1 in 1919 did excellent work in determining the effect of grain size on the hardness of brass. About the same time Jeffries2 and Sykes3 ascertained the effect of grain size on the strength and ductility of several metals at temperatures ranging from 80°K. to their melting points. When creep was recognized as an important property of metals, those engaged in the study of this property tried to determine the effect of grain size4-9 on creep rates. Unfortunately, most of the investigations were conducted on only two grain sizes, often designated simply as "fine" and "coarse." It is well known that at high temperatures coarse-grained test bars creep less than fine-grained bars. The relation between grain size and size of test bar, however, has been frequently overlooked. In his early work, Jeffries2 showed that the number of grains in the cross section has a more important influence on the properties of the material than the actual grain size. More recently Hanson and Sandfordl0 and Pell-Walpole,ll in their measurements of the creep and tensile properties of tin, tested a wide range of grain sizes and correlated the grain size with the strength. Hanson9 later established the relation between the number of grains in the cross section and the creep rate. At high temperatures, generally a coarsegrained structure is considered superior in creep to a fine-grained structure, but it is evident that for a given bar size continuously increasing the grain size will

Jan 1, 1944

By C. F. Riisness, E. R. Parker

That grain size has a great effect on the mechanical properties of metals has been recognized for a long time. Bassett and Davis1 in 1919 did excellent work in determining the effect of grain size on the hardness of brass. About the same time Jeffries2 and Sykes3 ascertained the effect of grain size on the strength and ductility of several metals at temperatures ranging from 80°K. to their melting points. When creep was recognized as an important property of metals, those engaged in the study of this property tried to determine the effect of grain size4-9 on creep rates. Unfortunately, most of the investigations were conducted on only two grain sizes, often designated simply as "fine" and "coarse." It is well known that at high temperatures coarse-grained test bars creep less than fine-grained bars. The relation between grain size and size of test bar, however, has been frequently overlooked. In his early work, Jeffries2 showed that the number of grains in the cross section has a more important influence on the properties of the material than the actual grain size. More recently Hanson and Sandfordl0 and Pell-Walpole,ll in their measurements of the creep and tensile properties of tin, tested a wide range of grain sizes and correlated the grain size with the strength. Hanson9 later established the relation between the number of grains in the cross section and the creep rate. At high temperatures, generally a coarsegrained structure is considered superior in creep to a fine-grained structure, but it is evident that for a given bar size continuously increasing the grain size will

Jan 1, 1944

By D. B. Crouch, D. A. Poulter

The engineering and metallurgical assessment of the McLaughlin Project ore body concluded that an open-pit mine and cyanide leach mill process would be feasible, producing both waste rock and residual mill tailings. As a part of the planning and permitting process, site selection studies were conducted for the tailings and waste rock disposal. The site selection process began with a regional identification of potential disposal sites and proceeded through 1) regional screening, 2) elimination of sites with obvious fatal flaws, 3) qualitative ranking of site evaluation criteria, 4) quantitative ranking of sites, 5) field investigation, 6) evaluations of field data, and 7) selection of preferred sites. Based on this approach of site rankings and field evaluations, tailings and waste rock disposal sites were selected and recommended for the preliminary design phase of the permitting and project development process. The site selection study provided the documentation necessary to justify the use of these sites for waste disposal and enabled Homestake Mining Co. to anticipate and integrate environmental concerns with agency requirements into the planning process.

Jan 1, 1986

By D. C. Shelton

Eq. 4 and 5 on page 5 of the March 1965 issue of Transactions, and Eq. 12 on page 8 of the same issue should read respectively:

Jan 1, 1965

By Charles Will Wright

ALTHOUGH the United States has long led all other countries in both the production and consumption of mineral products, the trend seems definitely toward an increasing dependence upon foreign sources of supply. This is not to take the position that we are either a have or a have-not nation. For years we shall continue to secure a large proportion of our needed minerals: from our own mines, but we must face the fact that this century has seen "a more thorough and intense development of the mineral resources of the United States and a greater depletion of its irreplaceable mineral reserves than has occurred in most other countries. An audit of our mineral production given in the attached charts discloses the extent of our deficiencies. Because of these facts, low-cost foreign sources offer a promising field for the investment of a portion of our mining capital and an opportunity to obtain for the United States a greater supply of strategic metals and minerals. How. ever, to reach this end, the industrialist investing in the foreign field must have the full co-operation and strong backing of the Federal Government and the involved Federal agencies.

Jan 1, 1947

By C. Stansfield Hitchen

THE introduction of the logarithmic sector method of quantitative spectrography by Scheibe and Neuhäusser in 1928, and the subsequent .modification and improvement of the method by Twyman and Simeon, would seem to have marked yet a further advance in quantitative spec-trum analysis and its industrial application, inasmuch as it offers a simple means of eliminating some of the uncertainties inherent in the older methods based upon mere visual comparison of line intensities. In their recent admirable review of the position and capabilities of industrial spectroscopy, Brownsdon and van Someren1 say: Ways and means of facilitating the comparison of line-intensities so as to give them numerical values are helpful, and of these a logarithmic sector rotating in front of the slit appears to he one of the most promising; . . . the success recently experienced by the author in using this method for the examination of steels and solutions of metallic salts prompted him ,to investigate its possible use in estimating the impurities commonly present in crude and refined tin. The results of this investigation are submitted in the present paper. Details of a number of spectrographic analyses of tin for various impurities have already been published. Thus, Schweitzer2 describes the spectrographic examination of tin for lead, bismuth and cadmium, and was able to distinguish between such atomic percentages as 0.01, 0.05, 0.10, 0.30, 0.60, 1.20, 3.00 and 10.00. Negresco3 investigated the bismuth content of tin over a range of from 0.0005 to 35 per cent. Meggers, Kiess and Stimson4 compare spectrographic and chemical analyses of tin metal for copper, lead, iron, zinc, silver, nickel and bismuth. They stress also the value of spectrum analysis in the examination of tin used for boiler plugs, where the requirements that only minute quantities of impurities shall be present render the chemical analysis both tedious and difficult.

Jan 1, 1933

[Appalachian Petroleum Section: James M. Kimbrough, chairman; John H. Adair, first vice-chairman; Walter L. Diddle, second vice-chairman; Byron M. Finch, secretary-treasurer. Balcones Section: Robert V. West, chairman; Frank W. Jessen, first vice-chairman; Zane V. Morgan, second vice-chairman; Brantley G. Myers, secretary-treasurer. Meets 4th Wed., Petroleum Club (San Antonio) or Terrace Dining Room (Austin) Billings Petroleum Section: Charles B. Evans, chairman; L. M. Lyon, first vice-chairman; Gordon E. Lansford, second vice-chairman; Fred. A. Haddenhorst, secretary-treasurer. Meets 3rd Tues., Billings Petroleum Club. California Coastal Section: Robert L. Richardson, chairman; David K. Hayward, first vice-chairman; W. Jackson Bransford, secretary; William N. Harwell, treasurer. Meets 3rd Thurs., Pierport Inn, Ventura. Caracas Petroleum Section: Edwin A. Moo re, chairman;. Jose Cirigliano, vice-chairman; Frank B. Davis, secretary; Robert N. Powers, treasurer. Meets 2nd Tues., Caracas Theater Club.]

Jan 1, 1961

All the TECHNICAL PUBLICATIONS and CONTRIBUTIONS published in 1940 are available at Institute headquarters, unless otherwise noted. They are also on file in many public, university and technical libraries and, when so indicated in the list, may be found in the TRANSACTIONS. TECHNICAL PUBLICATIONS in Classes A-Metal Mining, B-Milling and Concen-tration, H-Industrial Minerals, and I-Mining Geology are distributed in MINING TECHNOLOGY, which is issued every other month. Technical Publications in Classes C-Iron and Steel Division, D-Nonferrous Metallurgy and E-Institute of Metals Division are distributed in METALS TECHNOLOGY, which is issued twice quarterly. TECHNICAL PUBLICATIONS in Class G-Petroleum Division are distributed in PETRO-LEUM TECHNOLOGY, which was issued quarterly in 1940 but will be issued every other month in 1941. TECHNICAL PUBLICATIONS in Classes F-Coal Division, J-Mineral Industry Education Division, K-Mining Administration, and L-Geophysical Methods of Exploration are issued as separate pamphlets. An Institute member is entitled to one copy of any TECHNICAL PUBLICATION or CONTRIBUTION. Copies of TECHNICAL PUBLICATIONS listed have been mailed to members of the Institute accord-ing to their registration by classes. CONTRIBUTIONS and other TECHNICAL PUBLICA-TIONS will be sent upon request. A member may purchase an additional copy of a TECHNICAL PUBLICATION or a CONTRIBUTION at one cent a page; minimum charge, 25¢. Nonmembers may purchase any CONTRIBUTION or a TECHNICAL PUBLICATION of the F, J, K, or L classes at the same rate, but the nonmember price per copy for METALS TECHNOLOGY, MINING TECHNOLOGY or PETROLEUM TECHNOLOGY is $1.25 domestic, $1.35 foreign countries. TECHNICAL PUBLICATIONS (separate pamphlet form), $2 per annum domestic, $2.50 foreign. METALS TECHNOLOGY, $7 per annum domestic, $7.80 foreign (Iron and Steel Division and Institute of Metals Division ferrous and nonferrous papers). MINING TECHNOLOGY, $6 per annum domestic, $6.60 foreign (metal mining, milling and concentration, Industrial Minerals Divi-sion, and mining geology papers.) PETROLEUM TECHNOLOGY, $6 per annum domestic, $6.60 foreign. Bound volumes have been mailed to members that have requested them, and MINING and METALLURGY is mailed each month. A member is entitled to one volume a year on his membership and he may purchase for $2.50 one copy of a volume not already received; additional copies of the same volume, $5. Nonmembers may pur-chase the volumes listed, at $5 each, plus 60 cents for Canadian or foreign postage. Extra single copies of MINING AND METALLURGY, 25¢ current issue, back numbers 50¢ each to members; to nonmembers 506 current issue and $1 each, back issues. Subscription price to nonmembers and to members for extra copies, $3 per annum domestic, $4.00 foreign.

Jan 1, 1940

By Frank R. Van Horn

It is customary to ascribe two general modes of occurrence to natural gas, namely, shale gas which, as the name indicates, is found in shale, and reservoir gas, which occurs in sandstone, conglomerate and dolomitic limestone. Both of these types are found in the Cleveland district. The shale gas has been produced on a small scale for a long period of years, probably dating back as far as 1883. Shale gas is a low-pressure gas, small in volume with variable pressure, and is limited to no definite horizon. It is generally independent of oil, may last for a long time, and is not dependent to any great extent on the structure of the rocks. There are many such wells in the district which range from 400 to 1,840 ft. in depth, although most have been completed at about 800 ft. This indicates that the wells pass through the Cleveland and Chagrin shales into the Huron or Portage shale of the Upper Devonian. During the last 2 years great interest has developed in a deeper-seated reservoir gas. What is commonly called reservoir gas is generally a high-pressure gas occurring in large volume at a definite horizon. Oil may, or may not, be associated with the gas, and in most regions in which reservoir gas is found, the geological structure is of great importance. This type of gas occurs in all large fields such as those of West Virginia which have been supplying Cleveland until the recent discovery of local gas at great depths in commercial amounts. Historical Outline The oldest well producing reservoir gas in the district was drilled in 1886 in Newburg for what was then known as the Cleveland Rolling Mill Co. This well was 3,000 ft. deep, and was thought to have reached the "Clinton" formation. Two "sands" showing small amounts of oil were recorded in the Niagara limestone at depths of 2,658 and 2,686 ft. This is about the horizon of the so-called Newburg sand which has proved to be of some importance as a source of gas and oil by recent drilling operations. The rock pressure was reported to be 400 to 500 lb. per square inch, but since the volume was only 14,000 to 16,000 cu. ft. daily, the well was not only considered unsuccessful but was thought to prove the absence of high-pressure gas in commercial quantities in the Cleveland district.

Jan 1, 1917

By Peter Greenfield, Paul A. Beck

Thirty binary systems of vanadium and chromium group transition elements with second and third long period transition elements were explored in regard to the intermediate phases formed. It was found that the phases predominating in these systems are s, AB type with ordered a-tungsten or C8 structure, close-packed-hexagonal with small unit cell dimensions and, finally, phases isomorphous with 1-manganese. IN recent years, considerable information has become available concerning the intermediate phases in binary systems of the transition elements. Thus, the s phase has been found to occur in most of the binary systems of vanadium, chromium, and molybdenum with the group of elements manganese, iron, cobalt, and nickel.' It was observed that, while the rr phases formed by chromium with manganese, iron, or cobalt possess a considerable temperature range of stability, particularly in the Cr-Co system, the corresponding s phases with molybdenum are limited to a temperature range of less than 400" above about 1200°C. Goldschmidt' reported v phases of tungsten with iron and cobalt, and these are apparently stable only at (and above?) 1400°C." Exploratory work in this laboratory with Fe-W and Co-W alloys of approximately 60 atomic pct W annealed at 1300°C did not produce X-ray patterns suggesting the presence of a phase. It appears then that the phases of iron and cobalt with the chromium group elements decrease in stability as the two components are chosen from long periods further removed from each other. From the available information, it might be concluded that the controlling factor is the increasing difference in atomic radii between the components. In contrast to the a phase, the phases formed by iron and cobalt with chromium group elements' are stable only when the latter have large atomic radii (molybdenum and tungsten); the corresponding phases with chromium do not occur. When the difference in atomic size becomes still larger (r,/r,, approaching the ideal value of 1.225), the u and p phases are replaced by Laves phases (AB,), as in the alloys of iron and cobalt with columbium," tantalum." and titanium."-" However, atomic size certainly cannot be the sole determining factor, since, for instance, in contrast to the very stable (Mo, Co)p phase, no such phase occurs in the Mo-Ni system even though the atomic diameters of cobalt and nickel are nearly the same. Similarly, chromium and cobalt form a a phase in a wide temperature range," but the corresponding s phase in the Cr-Ni system is missing. It has been shown that the composition of the u phase in various binary and ternary systems of transition elements in the first long period may be correlated in a fairly quantitative manner with the number of electron vacancies. The influence of electronic structure is probably present also in binary and ternary phases' and to some extent, apparently, even in Laves phases." " Although the absence of phases in the Cr-Ni and Mo-Ni systems has not as yet been explained on the basis of electronic structure, it appears reasonable to suspect a connection. One of the great difficulties in arriving at well founded rules in regard to the alloying behavior of transition elements lies in the lack of reliable information concerning the details of their electronic structure in the metallic and alloy form. The theoretical penetration of this field appears to be beset by very considerable difficulties, even when the complications due to alloy formation are disregarded. Another great source of uncertainty is the scarcity of phase diagram information even for binary systems of the transition elements so that only a very limited basis is provided for generalizations as to the occurrence of intermediate phases. For instance, very few binary phase diagrams of second and third long period transition element systems have so far been published. The present work was undertaken in order to survey the various types of intermediate phases occurring in 30 binary systems of elements of the group vanadium, columbium, tantalum, chromium, molybdenum, and tungsten with the elements rhenium, ruthenium, rhodium, palladium, and platinum. For most of these binary systems phase diagrams are very incompletely or not at all known, as will be further reviewed.*

Jan 1, 1957