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By J. C. Miller

In offshore oil drilling as it is done today, accidental blowouts cause considerable damage lo the environment. Public alarm over such accidents has already resulted in a number of legislative proposals which appear to favor the cessation of all drilling on the Federally owned continental shelf. Present concern for the environment and the increasing water depths associated with offshore drilling suggest the desirability of applying underground mining technology to offshore petroleum exploration. If offshore drilling were to proceed from underground accesses to the continental shelf, accidental damage to surface waters would be avoided, and so would the difficulties of exploring in deep or ice-filled waters. The specific approach proposed here is intended as a preliminary to offshore oil exploration in a known field or geologic structure. The end result of this method would be an on-shore vertical or inclined shaft terminating in an operating tunnel or haulageway as shown in the illustrations. From the haulageway, branching access tunnels would lead to drilling compartments. With this arrangement, it appears likely that one operating tunnel could serve all lessees ill a particular unit operation. Although an inclined shaft is not illustrated, this would probably be more practical than a vertical shaft owing to the length of the casings and the character of other equipment used in oil producing operations.

Jan 1, 1971

By H. Van F. Furman

TO those engaged in the purchase and sale of gold- and silverores, mattes and bullion, the frequent differences in the gold- and silver-contents, as reported by different assayers, is a source of much annoyance and expense. The desirability of uniform methods of assay has long been recognized by certain refiners who specify in their bullion-contracts the method to be adopted in assaying the bullion. One large producer of base bullion employs at each refining-works with whom it has a bullion contract an assayer whose duty it is to see that the bullion is sampled and assayed according to contract-specifications. For the assay of gold- and silver-bullion, standard methods are now generally adopted; the reeult being that differences seldom occur. While we cannot hope for anything near perfection from fireassay methods for ores, mattes and base bullion, as carried out cornmercially, such methods may be made to yield results which answer all commercial requirements, and they will probably be retained for obvious reasons. The object of the present paper is to point out some of the sources of error and to show the importance of more uniform methods of assay and close attention to the details of the work. The sources of error in the assay of ores and mattes are: improper sampling; losses of the precious metals during fusion, scorification and cupellation; imperfect elimination of the base metals on the cupel and imperfect extraction of the silver during the parting in nitric acid. It is not the object of the present paper to enter upon the subject of sampling; but a few remarks may be of value. There has been considerable discussion recently in Colorado upon the frequent differences which occur in the assays of Cripple Creek gold-ores, and these differences have been attributed to various causes. The writer is informed by two of our most prominent smelters that since they have adopted 100-mesh screens (the general practice is 80-mesh) the

Jan 1, 1895

By K. J. Powers

The Mine Accident, Injury, Illness and Employment Database at the Mine Safety and Health Administration's Health and Safety Analysis Center is a computerized system that stores accident, injury, illness and employment data about all coal and metal/nonmetal mines in the United States. The paper discusses the system for collecting, storing, analyzing, and reporting this information and how these data are used in the ongoing effort to increase the health and safety in this nation's mines.

Jan 1, 1983

By D. W. Brunton

The erection of large metallurgical establishments for the treatment of gold, silver, copper, and lead-ores, at railroad arid topographical centers, where fuel and fluxes, together with proper oremixtures, can be cheaply and constantly obtained at all seasons of the year, has led to the very general introduction of a system of ore-handling known as "public sampling." By this system the ore, instead of being shipped direct to the mill or smelter, is sent to a public sampler, where it is crushed and sampled. Guaranteed samples are sent to the different metallurgical establishments, and the ore is then sold to the highest bidder. Though differing in many respects from the English system of "ticketing," the underlying principle is nearly the same, while the greater rapidity with which a lot of ore can be disposed of renders

Jan 1, 1885

By Gail F. Moulton

The production of petroleum in Illinois in 1928 was approximately 6,500,000 bbl., a decline of about 500,000 bbl. from the previous year and of about 1,500,000 bbl. from 1924. Production increased about 200,000 bbl. in Indiana to slightly less than 1,000,000 bbl. Production for 1929 is estimated at approximately 6,000,000 bbl. for Illinois and 1,000,000 bbl. for Indiana. Illinois Because production from most of the wells in the state has declined to a small daily average and the low prices for crude oil discouraged wildcatting, the number of wells drilled fell below that for any previous year since the development of commercially important production in the state. The Ohio Oil Co. discovered a pool of apparent commercial importance in southwestern Illinois near Dupo, in St. Clair County, and favorable showings of oil were encountered in a well in southeastern Illinois, near Harrisburg in Saline County. New production from the Dupo area is expected to check the rate of decline for the state. Thc following tablel summarizes field developments for 1927 and 1928 (for important detail by counties see notes at foot of table): 1027 1928 Completions........................................... 162 145a Initial production, bbl.................................. 2244 1840b Dry holes........................................,.... 66 58" Gas well completions................................... 13 8d 0111 wells abandoned.................................... 45" a Crawford, 44; Lawrence, 28; Wabash, 40. b Crawford, 501; Lawrence, 403; St. Clair, 165 (4 completions); Wahash, 668. o Crawford, 12; Wabash, 19. d Crawford, 6. b Lawrence, 21; Wabash, 15. The discovery well in the Dupo field in St. Clair County, produced about 150 bbl. per day from the Trenton lime at 660 ft. It is located in a northern extension of the Columbia-Waterloo anticline on which the Waterloo pool was developed in 1921. The best information on the.

Jan 1, 1929

By John Dilworth

IN considering the valuation of industrial properties in general, and of developed coal properties in par-ticular, it is assumed as fundamental that they have but one true value regardless of the object for which they are appraised. As regards developed coal lands, this value is only very approximately indicated by the recent sale price of neighboring lands, for the reason that it is rarely possible to find a sale of a coal property sufficiently similar in essential mining conditions to the one under consideration to serve as a measure of its value; and if such a one is found there are frequently incidental conditions peculiar to this particular transaction which invalidate the use of the sale price as a measure of general values. The true measure of the value of a coal mining opera-tion is the amount and rate of earnings it will afford with intelligent and experienced management. Prac-tically all of the features of a property which are gen-erally recognized as affecting its value relate either to the cost of producing the coal, or to the price it will bring, and so are intimately associated with earnings. In practice it is customary to appraise those portions of a developed coal property which are produced -by the industry of man-mine plant, equipment, development, town, etc.-at their cost of replacement at prevailing prices of materials, machinery, and labor, with such deductions for age, condition, obsolescence, and lack of usefulness as conditions warrant. Surface is appraised at the estimated cost of similar land in the district. Coal value is the difference between the worth of the entire property; considered as an industrial unit and

Jan 9, 1927

One of the very simplest losses to overcome, and at small expense, is belt slip. To show the extent of the loss of money through slipping of the main belt alone, a chart, supplied us through the courtesy of the Cling-Surface Co., Buffalo, N. Y., is shown herewith, upon which this is easily ascertained. By glancing up and down column "D" of this chart it is evident that the "Cost of Avoidable Belt Slip per Year in Dollars" may vary all the way from the smallest sums into the thousands of dollars. Roughly, 2 per cent. of the potential power in the driving pulley of the engine is represented by "belt creep." Its loss is unavoidable because of the elasticity of the belt. This has been recognized and provided for in the chart, so the reader can go ahead and connect known values, while the intersection with column "D" gives the avoidable money loss. Simply zig-zag across the chart twice with a straight edge, as shown by the dotted lines and the money loss is immediately found. Thus if the total belt slip is 6 per cent. (column A) and the cost of coal per ton is $4 (column B), run a straight line through those two points and locate the intersection with column "C." Then from that point of intersection run over to the tons of coal burned per year (which in this instance has been stated as 1000 tons) and the cost of avoidable belt slip per year is shown by column "D" as being $160. To give a clear idea as to the meaning of "Total Belt Slip Per Cent." let us take an example. You find by means of a revolution counter that a given driven pulley is rotating only 940 times per minute. You figure that without slip it should rotate 1000 times per minute; 60 revolutions per minute, therefore, are absolutely lost. Dividing this 60 by the r.p.m. that pulley should make you get 0.060 or 6 per cent. which is the "Total Belt Slip." After having made this determination, it is a simple matter to apply it to the chart as has been done and determine the money loss per year due to such slip.

Jan 4, 1918

By F. W. Maclennan

ORE production from the property of the Miami Copper Co. began early in 1911. Until 1925 this ore came from the so-called high-grade orebodies, which contained a little over 2 per cent. copper. This ore was mined by the following methods. 1. Top slicing after mining the peaks by square setting, which produced 4,524,347 tons, including ore from square setting. 2. Shrinkage stoping with sublevel caving of the pillars, which produced 2,230,577 tons. 3. Undercut caving with hand tramming, which, produced 15,427,672 tons. Estimating December tonnage, the total ore mined to the end of 1929 will amount to slightly more than 43,000,000 tons. The first method was described by E. G. Deane1 and the second by D. B. Scott,1 and the third, together with a general, description of the mine, by J. H. Hensley, Jr.1 The geology of the district has been worked out by. Dr. F. L. Ransome.2

Jan 1, 1930

By A. Bentzen, S. S. Wong, W. K. Fletcher, B. J. Price, A. J. Sinclair

One hundred eleven pyrite samples from three porphyry-type deposits in the Canadian Cordillera were analyzed (many in duplicate) by AA spectrophotometry for Co, Ni, Cu, Pb, Zn and Mn. All elements have density distributions that are lognormal or combinations of lognormal populations. Co and Ni in pyrites show zonal patterns that relate generally to mineralogical zones in the porphyry systems, particularly if contoured as the Co/Ni ratio. High Cu and Mn values in pyrites also correlate with Cu-rich mineralogical zones. Other elements studied appear less regular in their distribution patterns, although Pb and Zn highs in pyrite seem to occur sporadically near the margins of porphyry systems. These data considered with two other studies permit construction of an empirical model for the distribution of certain minor elements of pyrites from porphyry systems of the calc-alkalic suite. In particular cases pyrite geochemistry shows potential as an exploration tool to aid in target definition for detailed exploration.

Jan 1, 1978

WHILE papers on cleaning coal and mining coal were presented at the iron and steel and mining methods sessions, respectively, the first general session on coal was held on Wednesday afternoon. Howard Eavenson of Pittsburgh, Pa., as chairman of the session,* reported progress by the Committee on the Valuation of Coal for Blast-Furnace Coke. A paper on blasting coal effectively and safely in Southern Illinois, by J. E. Tiffany and S. S. Lubelsky, was abstracted and commented on by Dan Harrington, of the U. S. Bureau of Mines. W. J. German commented on some conditions mentioned in the paper as unsafe or bad practices, and added to these some further ex-amples; he made a strong plea for holes to be: drilled parallel to the bedding as the easiest way to determine the proper length or depth to agree, with the depth of kerf cut. Mr. Barron called attention to proper cutting and-drilling and rate of detonation of the explosive used, as effective aids in blasting coal. Another speaker mentioned an odd case where compressed black powder or "pellet powder," had decreased accidents at a non-gaseous mine where permissible explosives had been formerly used; the permissible cracked or shattered the roof, with a resulting high accident rate from falls of roof, and pellet black powder overcame this trouble. Eugene McAuliffe of the Union Pacific Coal Co. told of difficulties in changing from black powder to permissible in Wyoming mines. J. B. Dilworth read a paper on valuation of coal prop-erties, expressing a preference for the method of capi-talizing the earning power of a property. Eli T. Con-ner of Scranton, Pa., with much experience in valuation work, stated that the method was undoubtedly good, but many times failed because of inability to forecast accurately future earnings, and further contended that total valuation -and royalty rates could generally be fixed fairly when based on similar neighboring proper-ties' rates when these had recently been established by a free bargaining. S. A. Taylor of Pittsburgh, Pa., stated that a leasehold value could be fairly established by figuring based on 10 to 20 per cent of the profit resulting from operation. The chairman read a written discussion from Henry Louis of England, called atten-tion to differences in valuation resulting from whether gross or net profit or earnings were used as a basis for capitalizing. John A. Garcia of Allen & Garcia gave a most inter-esting account of coal mining and general conditions in Russia as noted in his recent extensive visit there, which appears elsewhere in this issue. Although agree-ing with most thinking Americans that government operation is incompatible with progress, he showed that mining conditions were far from impossible in present-day Russia. Charles E. Stuart gave motion pictures of parts of the trip, with, his own comments supple-menting those of Mr. Garcia.

Jan 3, 1928

By E. Stansfield

IT. has long been known that coal is unstable and oxidizes in air, even at ordinary atmospheric temperatures; also, that such oxidation affects the analysis of coal. Nevertheless little or no precaution is taken to prevent oxidation in the ordinary methods of analysis, and the possibility of error due to oxidation is sometimes ignored even in researches on coal. Although the general nature of coal oxidation is well known, and many workers have made careful studies of the rate of oxidation of different types of coal exposed to oxygen at different temperatures, yet the amount of oxidation coals undergo in the ordinary process of analysis, and its influence on the determined analysis, is not well known, and the published data are widely scattered through the literature. This paper is a collec-tion, from this laboratory, of data that bear on the subject, together with a brief summary of three methods employed here to evaluate the oxidizabil-ity of coal. The post-Carboniferous coals of Alberta range all the way from anthracite down to lignite. As some of them are notably susceptible to oxidation, the necessity for care was early forced upon our attention, and oxidation has been reduced either by the removal of air with a vacuum pump or by the displacement of air with natural gas (methane). The two routine analytical operations most liable to involve oxidation are the preliminary, partial drying of the crushed coal (called air-drying) and the determination of moisture. The first is a prolonged operation on coarse coal at ordinary temperatures, and the second a short treatment on powdered coal at higher temperatures. Oxidation also occurs in coal samples stored in ordinary sample bottles. In order to gain information for this study, determinations were recently carried out on the same samples in air, in natural gas, and in vacuo. Sixteen coals were tested; three would be classed in the United States as coking bituminous coals, two as noncoking, nonslacking, bituminous coals, and the rest as subbituminous. Table 1 gives typical analyses of these coals as mined.

Jan 1, 1934

By A.E. Martin, Gerhard Derge

IE the molecular constitution of molten slags were better known, the nature of chemical reactions in slags and between slags and metals could be better understood and as a consequence might be better controlled. Constitutional information can be obtained by studies on either the molten or the solidified slags. Valuable as the studies on solidified slags admittedly are for many purposes, especially as control methods in steelmaking, they are always of questionable value in giving information on the molecular constitution of liquid slags. However, the characteristics of molten slags such as viscosity, rates of dilfusion, and electrica1 conductivity can be determined experimentally and interpreted along with other knowledge on slag-metal and slag-gas reactions so as to provide direct information on liquid slags. Metallurgists are accustomed to regard reactions in molten slags as involving only neutral molecules, whereas it is quite possible that ionic constituents are actually involved. For example, the dissociation of calcium silicate usually is represented us Ca2SiO4 = 2CaO + SiO2 although a reasonable alternative would be to write Ca2SiO4 = 2Ca+2 + Si04-4 Such ionic dissociation has been suggested frequently without adequate experimental proof. This paper deals especially with electrical conductivity measurements on slags oi the blast-furnace type. These measurements were made to determine whether or not slags are ionized and, if so, to provide a qualitative estimate of the extent of ionization. Electrolysis experiments that indicate the identity of the ions present are also reported. Since the presence of ions has not been considered carefully in modern slag studies, the relevant literature will be reviewed. Review of Literature In 1906 Aikenl obtained a patent for a continuous process of producing iron electrolytically by passing a direct currenl through a bath of FeO.SiO2 to which iron oxide was added periodically to maintain a uniform concentration. The patent also included the addition of CaO and MgO to the bath to lower its melting point. The silicate melts involved were thus in the same system as basic open-hearth slags but with higher FeO and lower CaO contents. Electrical conductivity measurements were made on some molten silicates by Doelter2 in 1907. Natural silicates, such as

Jan 1, 1943

By A. E. Martin, Gerhard Derge

IE the molecular constitution of molten slags were better known, the nature of chemical reactions in slags and between slags and metals could be better understood and as a consequence might be better controlled. Constitutional information can be obtained by studies on either the molten or the solidified slags. Valuable as the studies on solidified slags admittedly are for many purposes, especially as control methods in steelmaking, they are always of questionable value in giving information on the molecular constitution of liquid slags. However, the characteristics of molten slags such as viscosity, rates of dilfusion, and electrica1 conductivity can be determined experimentally and interpreted along with other knowledge on slag-metal and slag-gas reactions so as to provide direct information on liquid slags. Metallurgists are accustomed to regard reactions in molten slags as involving only neutral molecules, whereas it is quite possible that ionic constituents are actually involved. For example, the dissociation of calcium silicate usually is represented us Ca2SiO4 = 2CaO + SiO2 although a reasonable alternative would be to write Ca2SiO4 = 2Ca+2 + Si04-4 Such ionic dissociation has been suggested frequently without adequate experimental proof. This paper deals especially with electrical conductivity measurements on slags oi the blast-furnace type. These measurements were made to determine whether or not slags are ionized and, if so, to provide a qualitative estimate of the extent of ionization. Electrolysis experiments that indicate the identity of the ions present are also reported. Since the presence of ions has not been considered carefully in modern slag studies, the relevant literature will be reviewed. Review of Literature In 1906 Aikenl obtained a patent for a continuous process of producing iron electrolytically by passing a direct currenl through a bath of FeO.SiO2 to which iron oxide was added periodically to maintain a uniform concentration. The patent also included the addition of CaO and MgO to the bath to lower its melting point. The silicate melts involved were thus in the same system as basic open-hearth slags but with higher FeO and lower CaO contents. Electrical conductivity measurements were made on some molten silicates by Doelter2 in 1907. Natural silicates, such as

Jan 1, 1943

By Arthur T. Ward

DESPITE the intense preoccupation of most of those members connected with the mining, concentration, and reduction of iron ores, the luncheon and subsequent technical session of the Eastern Magnetite Committee were exceedingly well attended. Many of the older faces were absent, but new ones took their places. More than sixty, all told, took in the technical session. Chairman Crockett opened the session by calling upon Meredith E. Johnson, whose paper, with its accompanying graph, was in reality a comprehensive historical review of iron mining from colonial days to the end of 1941. with some notes on current expansion which indicates that New Jersey is destined to become a still more important. factor in the production of magnetite ores.

Jan 1, 1942

By Harry Seltz, J. C. DeHaven

InteRmetallic compounds are formed in many binary metal systems. Some compounds are stable to their melting points, and others decompose at lower transition temperatures. Even those of the first class are dissociated in the liquid state, as indicated by the continuous form of their solubility curves at their melting points1. While the lattice structures of some of these compounds have been determined, their thermodynamic properties have not been investigated. In this paper is described the determination of the free energy and heat of formation of the compound CdSb, which is of the first class mentioned above, melting congruently at 455' C. This compound shows a rhombic structure, and the lengths of the edges of the elementary cell containing four molecules are: a = 6.52, b = 8.60, c = 4.16 A.' There are three possible methods of determining the free energy of formation of a compound of this type. The first method, applying the third law of thermodynamics, requires the measurement of its heat capacity preferably to liquid hydrogen temperatures, and a calorimetric determination of its heat of formation. The second method involves the study of the equilibrium of the compound in some gas reaction, such as: CdSb + CO² = CdO + CO + Sb From the known free energies of formation of CdO, CO² and CO the free energy of formation of CdSb could be calculated. The third method measures the electromotive force of a galvanic cell in which the cell reaction is the reversible formation of the compound from the elements. The first method is generally applicable, but requires elaborate experimental equipment. The second method can not be used for compounds melting at low temperatures, owing to the difficulty in establishing equilibrium. The electromotive force method, therefore, seemed to offer

Jan 1, 1935

By J. C. DeHaven, Harry Seltz

InteRmetallic compounds are formed in many binary metal systems. Some compounds are stable to their melting points, and others decompose at lower transition temperatures. Even those of the first class are dissociated in the liquid state, as indicated by the continuous form of their solubility curves at their melting points1. While the lattice structures of some of these compounds have been determined, their thermodynamic properties have not been investigated. In this paper is described the determination of the free energy and heat of formation of the compound CdSb, which is of the first class mentioned above, melting congruently at 455' C. This compound shows a rhombic structure, and the lengths of the edges of the elementary cell containing four molecules are: a = 6.52, b = 8.60, c = 4.16 A.' There are three possible methods of determining the free energy of formation of a compound of this type. The first method, applying the third law of thermodynamics, requires the measurement of its heat capacity preferably to liquid hydrogen temperatures, and a calorimetric determination of its heat of formation. The second method involves the study of the equilibrium of the compound in some gas reaction, such as: CdSb + CO² = CdO + CO + Sb From the known free energies of formation of CdO, CO² and CO the free energy of formation of CdSb could be calculated. The third method measures the electromotive force of a galvanic cell in which the cell reaction is the reversible formation of the compound from the elements. The first method is generally applicable, but requires elaborate experimental equipment. The second method can not be used for compounds melting at low temperatures, owing to the difficulty in establishing equilibrium. The electromotive force method, therefore, seemed to offer

Jan 1, 1935

By N. J. Gran, W. R. Opie

HYDROGEN in molten aluminum and aluminum alloys, which precipitates during cooling and solidification, is the principal cause of pin hole porosity in ingots and castings. Much attention has been given to determining the effect of temperature and pressure on the solubility of hydrogen in pure aluminum, but little data are available on hydrogen solubility in aluminum alloys. This investigation was undertaken to check results reported for pure aluminum and to show the effect of silicon and copper additions on the amount of hydrogen contained by molten alloys. Previous determinations of the solubility of hy-drogen in molten pure aluminum are plotted in fig. 1. The most reliable data appear to be those of Ransley and Neufeldl and of Baukloh and Oester-len.' The latter authors also report some results on the effect of copper and silicon additions. Up to 6 pct these elements decrease the solubility of hydrogen quite rapidly, with a definite minimum noted at 6 wt pct for both copper and for silicon, although no reason is apparent for these minima. Experimental Procedure The solubility of dry hydrogen in pure aluminum, aluminum-silicon, and aluminum-copper alloys was determined by the method of Sieverts.8 This consists of determining the volume of the gas system above the molten metal at a given temperature and pressure by using an insoluble gas. This volume is referred to as the "hot volume." The system is then evacuated and the soluble gas is introduced at the same temperature and until the same pressure is reached. It is necessary to introduce enough of the soluble gas to fill the space above the metal plus the soluble amount. The difference in the volume of soluble gas and the "hot volume" is the solubility. The accuracy of solubility measurements by the Sieverts' method is primarily depend-

Jan 1, 1951

By Charles Wright

AT most mines where large tonnages are handled, "bulldozing" or secondary blasting is an important and costly operation. To reduce the large blocks from primary blasting operations or stoping so that they will be small enough to pass through the chutes into the cars at the haulage level, and not too large for the crushing plant, requires blasting. Often this is done by placing a few sticks of dynamite on top of a block with or without a capping of mud, but to consume less dynamite and to promote safety, most secondary blasting is now done by blockholing, or the drilling of holes 6 to 12 in. long in the blocks, using only a part of a stick of dynamite per hole. Regardless of the method of blasting, however, the term "bulldozing chamber" is applied to the room where this work is done. Bulldozing chambers permit secondary blasting at all times in a safe place without disturbance to the other mining operations. The chambers are usually high above the haulage level and well below the stope level or open-pit floor. In most instances the material is passed through a grizzly in the bulldozing chamber, but sometimes no grizzlies are used. One to four raises extend from the chamber to the stope floor and one or two from the haulage level to the chamber floor. Occasionally large slabs of ore or rock choke the raises above the bull-dozing chamber, and these have to be blasted by attaching a bundle of dynamite sticks on the end of a long pole and placing them up in the raise between the pieces causing the choke. This is called "chute-blasting." To give a picture of the progressive developments in the use of the bulldozing chamber, a few typical mines that show the application of this method to both metal and limestone mines have been selected for description here. Limestone mines have been included because many metal miners do not realize to what extent the nonmetallic, or rock, miners are now applying metal-mining methods successfully in their operations. The bulldozing chamber is the "neck of the bottle" for some mines.

Jan 1, 1935

By Wesley G. Josephson

THE MINING PROPERTY of the Argonaut Mining Co., Jackson, Calif., is one of the oldest on the Mother Lode. A vein outcropping on a hill in this section could not long elude the eye of the forty-niner, so it was first discovered in 1850. From that time until 1893 the Pioneer mine, as it was then called, limped along under various poorly equipped and financed operators who tried tapping it by trenching and tunneling. Then the Argonaut Mining Co. took over the property and sank the present 65° inclined shaft in the hanging wall of the vein. The mine workings have now reached the 6000-ft. level, which is 5283 ft. vertically below the surface, or just 3 ft. over a mile. The total production of the mine is uncertain, because of lack of early records, but from 1893 to 1932 it is known to have produced in excess of $17,000,000.

Jan 1, 1932

By R. F. Mitchell, G. F. Dillon, A. F. Armington

In this paper the present methods of boron preparation are discussed with emphasis on the iodide intermediate. Several methods of boron triiodide preparation were investigated, the most satisfactory method being the preparation from the elements. A yield of 60 pct based on iodine is found for this method. Zone-refining, sublinzation, distillation, and fractional-recrystallization results are given for the boron triiodide, with distillation producing the best results. Several methods of decomposition are also discussed. The purity of the resulting iodide boron approximates the puritjl of the best available bromide boron, ELEMENTAL boron has been suggested as a possible high-temperature semiconductor by several workers,' but has never been exploited as a device material. The principal difficulty with boron is the unavailability of pure crystalline material from which accurate information on electrical properties could be obtained. Most boron crystals presently produced are very imperfect in structure and of questionable purity, particularly in relation to carbon content. Several methods of boron purification have been reported in the past few years, all of which produce material with a purity better than 99.0 pct. Most of these methods have been the subject of a recent review by Starks' and will not be elaborated upon in this report. However, of all the purification methods reported, only those using halide intermediates produce a purity approaching that usually required for electronic applications. The bromide intermediate has been most used for the preparation of high-purity boron.'y3 This material is easily prepared from the elements and can be effectively purified by distillation and decomposed by hydrogen reduction. The resulting product contains a trace of silicon, and an uncertain amount of carbon, believed to be approximately 100 ppm. It has been recently reported by Russian workers that high-purity boron can be produced using an iodide intermediate.' In the work cited, boron is reported free of spectro-scopically determined impurities, but the reported detection limits are quite high (- 100 ppm). In addition, no data is given on the carbon content of the product. In the present paper, boron triiodide was chosen as the intermediate for several reasons. First, carbon tetraiodide, which could be a major impurity, is reported to be unstable above 200" and hence could be easily separated from the boron triiodide by its decomposition, since temperatures greater than this are attained during the purification process. The low melting point (45°C) and boiling point (20B°C) and the relatively high vapor pressure of boron triiodide should allow the application of any physical purification technique to the material. The possibility of a lower decomposition temperature than that used for the bromide process is another advantage which might cut down extraneous contamination. The iodide, however, does have certain disadvantages when compared with the bromide, the production cost being the most significant. This is the result of a higher halide-to-boron weight ratio, which means more intermediate must be employed. The cost of the starting material is also greater for the iodide. This cost could be considerably reduced however, by recycling the iodine byproduct. Epitaxial growth of boron, which is probably the best method of producing junctions, should be possible with either the bromide or the iodide as the intermediate. However, this has been attempted only on a limited scale up to the present time because of the unavailability of good crystals. The authors have been relatively successful in laying down a heterotaxy of boron on silicon, however. This will be reported at a later date. Several crystalline modifications have been reported for boron, four of which are now believed to be real.' These are the a! and 0 rhombohedral and the a, and 0 tetragonal. In general, the a! rhombohedral is the low-temperature form and the B rhombohedral is the high-temperature form. The tetragonal structures are detected between 1000"

Jan 1, 1964