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By H. O. McLeod, J. M. Campbell

This paper presents the results of the data obtained in the first stage of a long-range study at high pressures of the system, vapor-hydrate-water rich liquid-hydrocarbon rich liquid. The data presented are for the three-phase systems in which no hydrocarbon liquid exists. Tests were performed on 10 gases at pressures from 1,000 to 10,000 psia. One of these was substantially pure methane, and the remainder were binary mixtures of methane with ethane, propane, iso-butane and normal butane. Several conclusions may be drawn from the data. 1. Contrary to previous extrapolations, the hydrocarbon mixtures tested form straight lines in the range of 6,000 to 10,000 psia which are parallel to the curves for pure methane, when the log of pressure is plotted vs hydrate formation temperature. 2. The hydrate formation temperature may be predicted accurately at pressures from 6,000 to 10,000 psia by using a modified form of the Clapeyron equation. The total hydrate curve may be predicted by using the vapor-solid equilibrium constants of Carson and Katz' to 4,000 psia and joining the two segments with a smooth continuous curve between 4,000 and 6,000 psia. 3. The use of gas specific gravity as a parameter in hydrate correlations is unsatisfactory at elevated pressures. 4. The hydrate crystal lattice is pressure sensitive at elevated pressures. INTRODUCTION Prior to 1950 many studies had been made of the hydrate forming conditions for typical natural gases to pressures of 4,000 psia.""'"'"" Most of these attempted to correlate the log of system pressure vs hydrate formation temperature, with gas specific gravity as a parameter. One of the more promising correlations was made by Katz, et al, which utilized vapor-solid equilibrium constants. The only published data above 4,000 psia are those of Kobayashi and Katz7 for pure methane to a pressure of 11,240 psia. In the intervening years, most published charts for the high-pressure range have represented nothing more than extrapolations of the low-pressure data, with the methane line serving as a general guide. The reliability of these charts has become increasingly doubtful (and critical) in our present technology as we handle more high-pressure systems. The portion of our high-pressure hydrate research program reported here was designed to: (1) investigate the reliability of existing charts; (2) obtain actual data on gas mixtures to 10,000 psia; and (3.) develop a simple hydrate correlation that was more reliable than those which simply used specific gravity as a parameter. Binary mixtures of methane and ethane, propane normal butane, or iso-butane were injected into a high-pressure visual cell containing an excess of distilled water. Hydrates were formed and then melted to observe the decomposition temperature of the hydrates at pressures from 1,000 to 10,000 psia. EQUIPMENT The equipment consisted of a Jerguson 10,000-lb high-pressure visual cell, a 10,000-1b high-pressure blind cell and a Ruska 25,000-1b pressure mercury pump. The visual cell was placed in a constant-temperature water bath controlled by a refrigeration unit and an electric filament heater. A Beckman GC-2 gas chromatograph was used in analyzing the gas mixtures after each run was completed. EXPERIMENTAL PROCEDURE After evacuating the gas system, the heavier hydrocarbon was injected into the high-pressure mixing cell to that pressure necessary to give the desired composition. This cell then was pressured to 1,100 to 1,200 psia by methane from a high-pressure cylinder. The mixing cell holding the gas contained a steel flapper plate and was shaken intermittently over a period of 15 minutes. After mixing, the valve to the high-pressure visual cell containing excess distilled water was opened, and the gas mixture was allowed to flow into the cell. The temperature in the water bath was lowered 10" to 15'F below the estimated hydrate decomposition point. As a first check, the temperature was increased at a rate of 1°F every six minutes to find the approximate point of decomposition. It was again lowered 1.5° to 5°F to form hydrates. The temperature was raised to within l° of the estimated decomposition point and then increased 0.2F every 10 to 15 minutes until the hydrates decomposed. This procedure was repeated at various pressures to obtain 7 to 13 points for each mixture between 1,000 and 10,000 psia. After completion of the hydrate decomposition tests, the gas mixture composition was analyzed with a calibrated gas chromatograph. These gas analyses have an estimated error of ± .1 per cent.

By BERNARD PLANNER

PRODUCTION COSTS, profits, and quality are the primary factors in the peacetime production of iron and steel. In a war emergency, as high production rates and as complete utilization of readily available raw materials as possible, consistent with securing passable quality, become the most important factors. In this connection a discussion of some of the recent developments in the German iron and steel industry, where the problem of scarcity has naturally always been more acute than in the U.S.A., maybe of interest. To get more pig iron out of the existing blast furnaces it was necessary to obtain the maximum efficiency from the iron-bearing raw materials. This was achieved by eliminating all "excess baggage," chiefly by beneficiating the ore. The preparatory work for this was done by various methods which are effective when the ore either is too poor or contains too many impurities or too much gangue. Some of the beneficiation methods are well known, some are combinations of wet-mechanical, magnetic, roasting, sintering, and other treatments.

Jan 1, 1942

By C. E. MacQuigg

BY and large the education of the engineer has been conservative and the reasons for this are obvious. Quite properly it has been a tradition of engineering education that facts and not fancies must be adhered to. Without a doubt, those men who formed the mold of our engineering philosophy as much as it is possible for such molds to be established-rightly held the highest standards of intellectual honesty. Fortunately, it was unthinkable to them to temporize with untried theories and naturally the men whom they trained as engineering educators carry this philosophy in turn to their students, thus handing down the tradition of stability.

Jan 1, 1943

By W. H. Bassett

W H. BASSETT was elected first vice-president at . the executive session of the new Board on Tues- day afternoon. Karl Eilers, H. Foster Bain, Thomas T. Read, and H. A. Maloney were respectively re-elected as treasurer, secretary, assistant secretary and assistant treasurer. The new Executive Committee will consist of W. H. Bassett, Chairman, and Richard Peters, Jr., H. C. Bellinger, E. De Golyer, Edgar Rickard. The Finance Committee will be J. V. W. Reynders, Chair- man, Henry Krumb and H. G. Moulton. George D. Barron was reappointed Chairman of the Admissions Committee, and F. Julius Fohs put in charge of the Papers and Publications Committee.

Jan 1, 1929

By AIME AIME

ON March 14, the University of Tulsa was accepted as a member of the North Central Association of Colleges, which ranks Tulsa among the leading universities of the country. A. G. OIiphant recently donated to the new school of petroleum engineering a splendid collection of books on geology, valued at $25,000. Waite Phillips, an oil producer and chairman of directors of The Independent Oil & Gas Co., donated $150,000 for a petroleum engineering building

Jan 1, 1929

By AIME AIME

0 N March 5, at Carnegie Hall, Cleveland, the Ohio Section held a joint meeting with the Cleveland Engineering Society, and the local sections of the American Chemical Society, American Society of Mechanical Engineers, and the American Society for Steel Treating. Prior to the meeting there was an informal dinner attended by 50 men. Then followed an address, "The Principles of Corrosion Protection," by Ulick R. Evans, the well-known British specialist in this problem. There were 266 present, presided over by Zay Jeffries, president of the American Society for Steel Treating and a member of the Cleveland Engineering Society. The address was well received and some discussion followed

Jan 1, 1929

By AIME AIME

T HE Mid-Continent Section of the Petroleum Division met on Mar. 11 in the engineer's room of the Tulsa Building, Tulsa, Okla., for the purpose of reviewing the papers presented at the annual meeting in New York. L. G. E. Pignell, chairman and delegate to New York for the Mid-Continent Section, read a brief report giving the outstanding features of the various papers that were presented. He expressed regret that more members of the Division could not be present in New York to hear the interesting papers and discussions. It was his opinion that the various remedies presented for overproduction seemed rather theoretical and impractical and he recommended that the engineers come to the aid of some of the economists in giving more practical consideration to the overproduction problem.

Jan 1, 1929

By William G. Christy

EFFORTS at smoke abatement date back to the year 1273 in England when a law was passed prohibiting the use of "sea cole." The law was not enforced, so King Edward I, 33 years later, appointed a commission "to enquire of all such who burnt sea cole in the city or parts adjoining, and to punish them for first offense with great fines and ransomes, and for the second offense to demolish their furnaces." Many other commissions have since been named to investigate the smoke problem in England, but it still persists in many British cities. In the United States the movement to abate the smoke nuisance started in certain Middle Western cities, and has made considerable progress. Until recently, the coal-producing industry co-operated little in smoke¬abatement programs, taking the attitude that smoke elimination is the dealer's or user's responsibility; and the dealers, in turn placed the responsibility entirely on the user.

Jan 1, 1942

By B. C. Craft, Murray F. Hawkins, John R. Rayne

A reservoir mechanism of sulfur recovery by the Frasch process is presented. Improving the economic, of recovery appears to be largely a well, rather than a reservoir problem. A most important factor is the limitation of the lateral extraction of .sulfur about the wells due to the almost vertical .flow of the injected hot water. Model studies are described which confirin the mechanism of sulfur recovery by presently used methods. Studies on a five-spot system indicate improved econo171ics regarding recovery, recovery rate, therinal efficiency, and well spacing. INTRODUCTION Sulfur mining by the Frasch process is one of the most important methods of sulfur production. Developed by Herman Frasch in 1894, it enjoyed a rapid growth and presently supplies 40 per cent of the world's sulfur and about 80 per cent of the U. S. sulfur." The Frasch process of mining the underground native sulfur deposits involves melting the sulfur in place by introducing super-heated water into the sulfur bearing formations, and producing the sulfur as a liquid. Many problems are encountered in mining these native sulfur deposits, and sulfur production depends chiefly upon the nature of the sulfur deposit and the underground thermal efficiency of the heat transfer system. THE RECOVERY MECHANISM Sulfur is typically found in salt dome cap rock as crystal aggregates occurring within the cavities, seams, and pores of limestone and gypsum formations.' Sulfur-bearing limestone is typically cavernous, vugular, and fractured. Porosity averages about 20 per cent and sulfur saturation averages approximately 25 per cent by weight.1,15 Vhe sulfur bearing formations are very heterogeneous in nature and physical characteristics vary widely within small distances. Total cap rock thickness may vary from 50 to more than 1,000 ft, and net productive thicknesses from a few feet to a few hundred feet. In most cases the upper portion of the limestone formation is barren of sulfur, varying from 5 to 200 ft in thickness.1,15,33 The immediately overlying sediments and the underlying dense anhydrite formation provide permeability barriers to the flow of water from the cap rock section.'" Sulfur wells are drilled with conventional oilfield drilling rigs. Fig. 1 illustrates the casing program of a completed sulfur well. The cap rock sections are drilled with core bits and continuous core logs are recorded. After coring, the cap rock section is underreamed to a diameter of 9 7/8 in. The bottom of the 8-in. casing is welded closed and rests on the bottom of the drill hole, which extends through the cap rock to a few feet above the bottom of the sulfur-bearing formation. The 8-in. pipe contains 5 ft of 3/4-in. perforations on 6-in. centers and 15 ft of 1-in. perforations on 1-ft centers. The 20-ft perforated section is set opposite the lower 20 ft of the sulfur-bearing formation. The 4-in. sulfur pipe is set inside the 8-in. water line on a seat ring at the top of the 5-ft section of 3/4-in. perforations. The mining water, heated to about 330°F under a pressure of 250 psi, is forced down the annulus between the 8-in. and 441-1. pipes and through the 1-in. perforations to the sulfur-bearing formation. Compressed air, at 400 psi pressure, is supplied through a 1-in. air line near the bottom of the well to provide air-lift of the liquid

Jan 1, 1957

By John Jermain Porter

PAGE. I. INtroduction............ 191 I1. Derivation of Formula foR Fuel-RequiRements.... 192 1. Heat Available in the Hearth........193 a. Method of Calculation..193 b. Data for the Determination of Critical Temperature.. 195 2. Heat Necessary in the Hearth ...... 197 a. To Care for Slag..197 b. To Care for Pig-Iron...198 c. To Reduce Silicon........198 d. For Other Items.........199 3. The Effects of Rate of Driving ..... 199 4. Loss of Carbon Between Throat and Hearth.....201 a. Solubility of Coke..201 b. Carbon-Loss Due to Flux....201 c. Effects of Reducibility of Ore..202 5. The Formula as Used........203 III. The LImitations of the Formula........ 204 1. Through Effects of Irregular Furnace-Work.....204 2. Through Ratio Between Heat-Requirements in Shaft and Hearth. 20.5 IV. The Formula Applied to Actual Furnace-Records,.. 209 1. Description of Furnace-Stock........ 209 2. Furnace Dam..........210 3. Application of Formula..211 4. Average Furnace-Practice..213 V. Sources of Error........... 214 VI. SuggesTions for Practical Methods of Fuel-Economy... 215 VII. Efficiency as a Factor in Furnace-Management.... 219 1. The Efficiency Principle........ 219 2. The Application to the Blast-Furnace..220 I. Introduction. The heat-balance of the blast-furnace has been a favorite subject for discussion for many years. and its study has contributed much to our knowledge. and still possesses a certain academic interest. As a means of accounting for differences in fuel-consumption, however. it has failed utterly. and it is evident that we must look elsewhere for the means of accomplishing this end.

Jan 1, 1912

By Harrison Schmitt

DURING the past decade the writer has studied and mapped certain ore deposits and their structural associations in the states of Chihuahua, Durango, New Mexico and Arizona, and he believes that these deposits, with the exception of the manto-chimney, are representative of the principal types in the area of the states named. In this paper the deposits are described; then generalizations are drawn so far as seems appropriate. HANOVER, NEW MEXICO The Hanover; New Mexico, zinc deposits were briefly described by Lindgren and others,1 Paige2 and recently in more detail by Schmitt.3 These, the kind ordinarily called contact metamorphic, border the southern end of an oval area of granodiorite intrusive 3/4 mile wide and 2 1/2 miles long (Fig. 1). The granodiorite has intruded, folded, and metamorphosed sedimentary and igneous rocks, which range in age from pre-Cambrian to Upper Cretaceous. About 90 per cent of the ore has replaced coarse, recrystallized, pure, fossiliferous, lower Mississippian, nonmagnesian limestone (Hanover limestone) 110 ft. thick;4 about 75 per cent of it occurs in the upper 50 ft. of this horizon just below an 18-ft. lower Pennsylvanian shale bed, which lies on a locally inconspicuous unconformity representing upper Mississippian time. The orebodies show five shapes or attitudes, each dependent on a special structural situation: 1. Most of the ore occurs as podlike; thick lenslike or other "three-dimensional" shoots extending from top to bottom of the Hanover limestone and lying adjacent to the outer contact of a silicate zone largely of andradite, which follows the intrusive contact (Figs. 1 and 2).

Jan 1, 1933

By Tom Westgarth

As papers are placed before you upon large gas-engines in Belgium and Germany, it was considered that some information should be given upon the same subject in Great Britain. I therefore agreed to compile these notes, which I have made very short in view of the somewhat full nature of the other papers presented to this meeting, and considering the complete nature of the many publications which have been made recently upon the subject of large gas-engines. I give below Tables I. to VI., showing the number and particulars of large gas-engines which have been built or are building by British makers, and in view of the growing size of gas-engines I have concluded that engines of less than 500 h.p. cannot now he included in the category of large gas-engines, and therefore I have not considered engines under that power. Table I.—-" Oechelhauser " Type Gas-Engines. Built or Building by William Beardmore Co., Limited, Glasgow Indicated ! Engines. Horse-Power Type. Nature of Work. Gas Used. 6 2,500 Twin cylinder. Dynamo. Producer. 1 in Single cylinder. Rolling-mill. Producer. 4 1,250 Twin cylinder. Dynamo. Producer. 2 1,250 Single cylinder. Dynamo. Producer. 4 625 Single cylinder. Dynamo. Producer. 1 625 Single cylinder. Rolling-mill. Producer. 1 625 Single cylinder. Air compressor. Producer. 2 500 Single cylinder. Air compressor. Producer. 7 500 Single cylinder. Cement-mill driving Producer. Total, 28 engines ; 32,600 indicated horse-power. * Presented at the Joint Meeting of the Iron and Steel Institute and the American Institute of Mining Engineers, London, July, 1906, and here published under a mutual agreement between the Councils of the two Institutes.

Jan 1, 1907

By R. H. Richards

In October, 1891,I read a paper before the Institute on a "A HandTelescope for Stadia-Work" (Bans., xx., 732), and promised to report at an early date some results showing the degree of accuracy attained with the instrument. I am now able to report on these results and also on certain improvements that I have made in the target since the first paper was read. I may say that I prefer the title, "Prismatic Stadia-Telescope," to that used in my earlier paper, for while the instrument can be used with perfect satisfaction for short sights up to, say, 300 to 600 feet when held in the hand, it is impossible to read milch longer distances without the use of a tripod, as a steady support for the instrument. Results are here given upon four combinations of prism and telescope. No. 1. A telescope made by Alvan Clark & Sons, 3-inch objective, 28 inches focal length, magnifying 60 diameters, the prism covering half the objective: Feet measured Reading of Distance reduced Reeding of rod pro by tape. the rod. to feet. portional to 100 ft. 127.66 1.1825 100 .92629 211.35 1.9585 100 .92666 326.59 3.0265 100 .92669 484.88 4.4925 100 ,92652 606.91 5.6225 100 .92641 Average,,92651 The value of this prism therefore is .92651 feet on the rod for 100 feet of distance, or 1 foot on the rod corresponds to 107.931 feet of distance. No. 2. A Bardou telescope having a 1-inch objective, magnifying 20 diameters, and a prism covering half the objective:

Jan 1, 1893

By L. C. McCabe

THE object of the present investigation was to discover a physical basis for rank differentiation of coals, particularly the coals of the Illinois basin. Vitrain1 was selected as the most appropriate coal material to use in the investigation, because of its homogeneity and ease of acquisition and handling. Previous Investigations.-Hoffman and Jenker2 have shown that their index of reflection is a characteristic of coal rank and that the Leitz slit microphotometer may he used in determining the different intensities of reflection. Zhemchuzhnikov3 measured the luster of several Russian coals with a color analyzer and found that the degree of luster was indic-ative of rank. Luster-volatile matter curves based on data from Sucan and Donetz coals were satisfactorily used for determining the rank or volatile content of other coals after the luster strength was determined. In 1934 Fisher4 reported refractive indices of 1.76 for bituminous vitrain and 1.87 for semibituminous vitrain. Investigation of Angle of Polarization.-Early in the present investiga-tion several determinations of the refractive indices of the vitrains were made by immersing the minus 150 plus 200-mesh powder in oils. It was found that all the samples fell within the range 1.6 to 1.8. However, difficulty was encountered in securing oils in this high index range that were closely enough spaced to separate some of the coals. The writers made a number of determinations of the angle of maxi-mum polarization from the polished surfaces of the vitrains and derived their refractive indices by the procedure described in the follow-ing paragraphs.

Jan 1, 1937

By Charles W. Merrill

IF we follow the threads of the mining problems, upon which I have touched, we find them all leading to one great fundamental desideratum. The people of this State, of this Nation, and of this world must be brought to a better understanding of the basic nature of our industry-must be made more mineral-minded. It is my belief 'that there is not a man present among this earnest gathering of those interested in the mining industry, who has not a deep-seated and heartfelt desire that the existing unprecedented welfare and prosperity of the whole mass of American people be maintained not merely through our own generation but through the generations of our children and their children. In the decades to come there can be no question of the keenness of the foreign competition which we are doomed to meet, and in this great international contest that Nation which has the best balanced program of development and that broadness of vision in its governmental direction, which recognizes the necessity of a sympathetic attitude toward the upbuilding of such a broad pro- gram will be the Nation which will maintain and pre- serve that welfare of all of its people.

Jan 1, 1929

By AIME AIME

NATURE was in a smiling mood on December 18, 1883. On that day, Chester Alan Fulton, the sixty-first President of the American Institute of Mining and Metallurgical Engineers, was born, and she endowed him with every good quality within her reach - looks, physique, intelligence, and character. Brought up in the valley of the Hudson River, with the mighty Palisades which make it the "Rhine of America," he has lived up to his early promise - as a man, as an engineer and as a friend.

Jan 1, 1943

By Milton F. Goodrich

The idea of using water-only cyclones to scalp clean coal from the feed to other devices has recently been gaining in popularity. 1,2,6 An indication of this popularity is that water-only cyclone scalping is already employed in a few commercial plants. Water-only cyclones scalp the feed to a heavy media vessel in the Warwick plant,3 to Deister tables in the Rowland plant,4 and to a heavy media cyclone circuit in the Amherst Coal Company's McGregor plant.5 Despite this trend, we found surprisingly little information in the literature on the performance of water-only cyclone scalping. Therefore, we undertook a study of its technical merits, limiting our investigation to a water-only cyclone scalper in conjunction with heavy-media cyclones. We felt this to be a reasonable combination of equipment, since both processes operate well on the same size coal. First, we developed simple mathematical relationships revealing general characteristics of the system. Next, we compared the clean coal yield and quality obtainable by the system on four different coals with that obtainable by heavymedia cyclone circuit alone and water-only cyclones middlings recirculation circuit alone. This was done by using computer program to simulate the operation of the three systems. Finally, we considered the effect that implementation of the system would have on a typical preparation plant circuit. The System The system chosen for study [(shown schematically in Fig. 1)] comprises two stages: a primary stage (PI) consisting of water-only cyclones, and a secondary stage (P2) consisting of heavy media cyclones. The water-only cyclones separate raw coal at a low specific gravity, producing a relatively small amount of high quality clean coal and a refuse containing much good coal. This refuse is then recleaned in the secondary stage, where the sharper separation of heavy media cyclones, operated at a higher specific gravity, reclaims additional clean coal. Finally, the clean coal from both stages is combined as the system's clean coal, while the refuse from the secondary stage becomes the system's refuse output. Theoretical Analysis Two assumptions lie behind the following theoretical analysis. The first assumption is that partition curves can represent not only the performance of each stage but also the performance of the system as a whole. These curves show partition number as a function of specific gravity, where partition number is either the percent or fraction of a raw coal with a given specific gravity reporting to clean coal. The second assumption is that these curves are independent of the raw coal characteristics. At any specific gravity the system's partition number is solely a function of the partition numbers of each stage. For convenience, we use the following variables in describing this relationship: g = specific gravity, PS(g) = the partition number of the system at specific gravity g, P1(g) = the partition number of the primary stage at specific gravity g, P2(g) = the partition number of the secondary stage at a specific gravity g. For this system, we can show algebraically that the relationship is: [Ps (g) = PI (g) + (1- P1(g)) P2 (9)(1)] With this equation the system's partition curve can be determined if the partition curves of each stage are known. By definition, the partition numbers P1(g) and P2(g) must each be less than, or equal to, one. Placing these constraints on Eq. (1), we arrive at the relations: [Ps(g) % P1(g) and Ps(g) % P2(g)(2)] Thus, at any specific gravity the system's partition number is always greater than that of both stages. [Figure 2] shows typical partition curves. Curve I represents the primary stage, which consists of water-only cyclones operating at a separating gravity of 1.3. (The separating gravity or the

Jan 1, 1979

US 4,181,520 - Direct reduction of iron oxide ore to sponge iron in a rotary kiln. Ore is fed into the kiln along with coal briquettes and passed through a preheating zone and then a reducing zone countercurrent to the flow of a kiln atmosphere which includes air or other oxygen-containing gas. The agglomerated coal is heated at such a rate that it disintegrates into fine particles in the preheating zone. The coal is largely recovered for reuse, while reduction is effected with a reducing flame rather than the coal. G. Reuter and W. Schnabel, assigned to Metallgesellschaft AG. Jan. 1, 1980. 6 pp. (75-36). Filed- 10-19-78 (952,870). Priority: West Germany, 1-14-75 (2,501,182). Same: British 1,532,969, dated Nov 22, 1978.

Jan 1, 1982

By W. D. Potter, E. T. Peters

Single-crystal films of boron have been prepared by thermal reduction of purified BCl3 with subsequent deposition of boron onto oriented silicon substrates. The structural properties of films prepared under various experimental conditions have been determined by light microscopy and "grazing-" angle electron-diffraction analysis. An orientation relationship is proposed for silicon and a-rhombo-heclral boron which can be described as: (111)Si (112)B; [110]Si [110]B ElEMENTAL boron is known to have a high energy gap* and consequently has potential value as a high- *Energy gaps of 1.35 to 1.55 ev1-3 and 2.0 ev4 are reported for ß-rhombohedra1 and a-rhombohedra1 boron, respectively. temperature semiconductor.5 Exploitation of this property, however, has been hampered by the unavailability of pure, single-crystal boron. Two recent symposia6,7 have treated the subjects of purification, crystallization, crystal structure, and properties of boron and provide a foundation for further investigation in these areas. The structure, lattice constants, and observed ranges of stability for four reported polymorphs of boron8°12 are listed in Table I. The rhombohedral structures are generally accepted as true polymorphs whereas the tetragonal structures are believed to be transient. Most currently available single crystals of boron are grown by Czochralski and floating-zone methods. Unfortunately, these crystals generally contain numerous defects and are highly strained as a result of the polymorphic transformations and thermal contractions which accompany cooling. Recently, Armington, Potter, and Tanner13 have reported the formation of single-crystal films of boron on silicon single-crystal substrates through thermal reduction of BC13 by hydrogen. Boron E. T. PETERS, Junior Member AIME, is Senior Scientist, ManLabs, Inc., Cambridge, Mass., and W. D. POTTER is Research Chemist, Air Force Cambridge Research Loboratories, L. G. Hanscom Field, Bedford, Mass. formed at temperatures near 1000°C was identified as the a-rhombohedra1 form, consistent with expectation. The present paper describes a continuation of this work with specific reference to characterization of the structural features of the deposited boron films. The ultimate goal of this program is to produce large-area single-crystal films of a-rhombohedra1 boron to be used for electrical and optical studies by other workers. PREPARATION OF BORON FILMS The experimental procedure of preparing thin films is similar to that described by Theuerer14 for the epitaxial growth of silicon by thermal reduction of SiC14 and has already been described as applied to the preparation of boron thin films.13 Briefly, a mixture of BCl3 vapor and dry hydrogen is passed over a heated silicon substrate. Thermal reduction of the BC13 allows deposition of boron on the substrate. The substrates were {111}-oriented, single-crystal silicon. Square specimens 0.63 cm on an edge by 0.1 to 3.0 mm thickness were prepared by

Jan 1, 1965

By Y. L. Yao

THE NaT1-type compound may be considered as the penetration of two diamond lattices in such a way that a superstructure of the bcc lattice is formed. Examples of the NaT1-type compound of lithium are LiZn, LiCd, LiA1, LiIn, and LiGa. Except for LiZn and LiCd, each molecule of these equiatomic compounds contains a total of four valence electrons. In LiZn and LiCd it was suspected (for example, see Ref. 1) that the fourth electron was withdrawn from the 18-shell of zinc or cadmium. An incomplete 18-shell would have to show strong paramagnetism. In 1955 Klemm and Fricke2 determined the magnetic susceptibility of LiZn, LiCd, LiA1, and LiIn (also NaTl and NaIn). The molar susceptibility of the outer electrons of LiZn and LiCd was found to be not strongly but weakly positive; that of LiAl and LiIn not negative but weakly positive. Thus they questioned the hypothesis about LiZn and LiCd in particular and the description of the NaT1-type structure in general. However, they did not determine the magnetic susceptibility of LiGa. This note is to report results for all five compounds of lithium. The starting materials are 99.9 pct pure lithium sticks containing less than 0.005 pct Na. 99.9 pct Zn, 99.9 pct Cd, 99.99 pct Al, 99.999 pct In, and 99.999 pct Ga. Weighed amounts of two components were wrapped in tantalum foil and placed in a graphite crucible. It was found that the tantalum sheath minimized the vaporization losses of lithium during melting. The sheath was easily stripped from the alloy rod and the tantalum in the alloy was barely detectable (less than 0.01 wt pct). The melting was performed in a resistance furnace under an argon atmosphere. Alloy specimens were annealed for 1 hr at 400°C in vacuum. The magnetic susceptibility at room temperature was determined by the Faraday Method, using the procedures previously described.' The results are shown in Table I. The interpolated values at 50 at. pct of Li and the average values at 48 to 52 at. pct of Li at 20°C determined by Klemm and Fricke2 are also shown. It is seen that the present value for LiZn and LiCd is slightly more positive but the present value for LiAl and LiIn is slightly less positive than their corresponding values. Also, it is noted there is an abrupt decrease of susceptibility of LiAl from 51.2 to 52.5 at. pct of Li. Klemm and Fricke2 found that the total susceptibility of LiZn, LiCd, LiA1, and LiIn is almost independent of temperature. slater4 gave a working expression for the diamagnetism of the atomic core as follows:

Jan 1, 1964