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By Walter C, Smith

Metallic bismuth was known in the Middle Ages and the name is supposed to come from the German Wismut. The origin of the German name is uncertain. References to bismuth are found in the writings of Valentine, Paracelsus, and Agricola between 1450 and 1550. Early specimens of bismuth were very impure and often were confused with antimony, tin, and zinc. About the middle of the eighteenth century, J. H. Pott, C. J. Geoffroy, and Torbern Bergman succeeded in producing fairly pure bismuth and showed it to be an elementary metal similar in many respects to lead.

Jan 1, 1953

By Roy A. Anderson, Roger H. McConnel

The Metaline district from 1906 through 1965 has produced nearly 16 million tons of ore yielding 400,808 tons of zinc and 178,062 tons of lead. The sediments, ranging from Precambrian into the Devonian, are schist, phyllite, conglomerate, greenstone, quartzite, limestone, dolomite, and carbonaceous slates. Quartz monzonite and granodiorite of the Cretaceous(?) Kaniksu batholith are exposed over a large area beginning a few miles south of the district. There is minor Tertiary conglomerate and basalt. Abundant glacial deposits obscure much of the bedrock. Northeasterly trending folds, having steep to overturned northwesterly limbs, and thrust faults, striking northeasterly and dipping southeasterly, characterize the deformation of the Precambrian and Paleozoic rocks. Recent drilling indicates that the Slate Creek fault, too, is also a southeasterly dipping thrust fault. This new evidence suggests that the Valley Block, like the other major structural blocks, may in part be a thrust plate rather than a graben, and that thus the district may have greater structural unity with the surrounding region than has heretofore been apparent. The Cambrian Metaline Formation of limestone and dolomite contains essentially all the lead-zinc mineralization. Most of the ore mined to date has come from a carbonaceous and irregularly siliceous breccia of sedimentary and diagenetic origin, locally called the "Josephine Horizon," that makes up the top few to 200 feet of the formation. The Josephine Unit is a breccia of gray limestone, coarse light gray dolomite, very thin-bedded, dark gray siliceous dolomite, and "zebra rock" believed to be of algal origin, embedded in a matrix of black dolomite or black jasperoid or some mixture of these two. The jaspcroid fragments and irregular blobs embedded in the black dolomite matrix and the jasperoid laminae in the very thin-bedded dark gray dolomite suggest that jasperoid was formed at the same time as the breccia matrix and as the laminated dolomite. So too, the marked tendency of sphalerite and galena to be disseminated mainly in the dark breccia matrix and their tendency to be most abundant in the jasperoid laminae of the very thin-bedded dark gray dolomite, even where the mineralized and laminated dolomite is fragmented and engulfed in black dolomite breccia matrix, suggests that in these ha bits the sulfides also were deposited contemporaneously with the sediments. Yet very commonly, veins and vague veinlets and patches of white quartz, usually carrying rather coarse sphalerite and sometimes galena crosscut all rock types. These contradictory relationships throughout the Josephine Unit suggest that both the black jasperoid and the sulfides were original constituents of the Josephine Unit but that, locally, they later were remobilized and deposited as white quartz and coarser grained sulfides. Possibly, at least in part, this "metamorphism" is one of the effects produced during or shortly after the intrusion of the Kaniksu batholith.

Jan 1, 1968

By R. E. Zimmerman

Wide attention is being placed upon various methods for cleaning the fine sizes of bituminous coals. The author describes and analyzes the results achieved on wet concentrating .tables of modern design on unclassified feeds of - 1/2 in. particle sizes, including tests on high-sulphur coals.

Jan 1, 1950

By C. A. Fisher

THE Salt Creek Oil Field of Wyoming occupies a unique position among the major oil fields of this country. Many years before the beginning of actual production in this area, in 1911, it had attracted country-wide attention as a district holding oil possi¬bilities. Even foreign capital, mainly French and Belgian, had sought out this district as having oil values and spent many thousands of dollars 'in an effort to acquire property rights' in this field which was very largely located on the public domain. Owing to inadequate laws governing the acquisition of oil lands on the Federal domain and a careless practice having grown up among oil land locators of that time, a complicated title situation quickly developed in Salt Creek. This condition of uncertain titles together with the isolation of the field from industrial centers were doubtless the two most potent factors in retarding its early development. After actual production began in 1911 governmental regulations, suits between the government, and the locator, disputed ownerships between locators and claim and counterclaim continued to retard the field's development. It is believed that the title situation in the Salt Creek Field, where potential values of such magnitudes were involved, was responsible more than any other factor for the ultimate passage of the government leasing act in 1920 affecting all oil lands on the Federal domain.

Jan 1, 1925

By AIME AIME

CHARACTERIZING the annual meeting as the biggest and best one yet has happened so repeatedly that some may suspect it has become a conventional phrase, like "good morning," and yet, what else can be said when not only one but all the many who express an, opinion use exactly those words, while the first of the two adjectives refers to a physical fact that is established by count. Perhaps there were hose who thought it not the best, but if so they were too tactful to say it out loud. So without further ado . let us admit that the one hundred and thirty-ninth general meeting of the A. I. M. E. held; as our By-laws provide, in New York during the third week of February, was the biggest and best of them all. Perhaps it is because we appreciate friendliness more as we grow older, but somehow the friendly atmosphere seems to rise slowly in temperature with the passing of the years. The actual atmosphere on the opening morning was quite the contrary, Feb. 17 being the coldest clay, so far, of this winter, and the suburbanites claimed that their thermometers had registered 5" below zero when they got up, though the official records of the weather man did not go that low. From that time the temperature steadily rose until Thursday afternoon, when the official record of 66" constituted a record high for Feb. 20 at New York. The weather man explained it by learned discussion of highs and lows, but we suspect the A.I. M. E. members must have had something to do with it.

Jan 1, 1930

By Donald L. Katz

FIFTEEN years ago Dr. Manning published a paper in "Petroleum Development and Technology" on '.Fundamental Research Relating to Petroleum." He tabulated for several industries "the proportion of their present success which can be fairly attributed to the application of information and processes obtained by scientific research," giving petroleum a score of 7 compared to 100 for the electrical and coal-tar industries. Today the petroleum industry as a whole and the producing groups both have raised their score beyond the majority and are climbing toward the top. Present practices are being developed both by fundamental research and the application of the research method in field operation.

Jan 1, 1941

By B. V. P. Rao, H. L. Lovell, G. Simkovich

In the study described here, flotation tests were conducted on pure CaF2, on CaF2 doped at several concentration levels with either NaF or YF3, and on natural fluorite samples containing various amounts of impurities in an effort to extend previous knowledge of the influence of crystalline point imperfections on the flotation properties of solids. The results of these tests showed that although recoveries generally decreased as impurities increased, the differences in recovery were not nearly as striking as those detected in earlier experiments. A number of experimentalists have shown an interest in the way in which crystalline point imperfections affect the flotation properties of solids. As long ago as 1953, Welch hypothesized that it might be possible to control surface imperfections and thereby also control the flotation of solids.' A few years later, in some rather extensive work, Plaksin and his coworkers varied the surface imperfections of a number of compounds by oxidation or reduction processes and found that significant variations in flotation properties resulted.2-4 More recently, Simkovich showed that the recovery of both AgCl and PbS could be markedly varied by adding solid-solution impurities, which acted as doping agents, to these compounds.5 Then Mular studied the flotation of ZnO as a function of the doping agents Al2O3 and Li2O.6 Once again, it was found that these impurities, even in very low concentrations, had profound effects upon flotation recoveries. From an imperfection point of view, the defect structures of the compounds tested previously are as follows:7 PbS — amphoteric semiconductor with a Frenkel-type defect structure in the cation sub-lattice.8 AgCl - ionic conductor-Frenkel type defect structure? ZnO — n-type semiconductor, zinc ion interstitials and quasi-free electrons.10 All of these works undoubtedly bear some relation to the findings that the flotation properties of seemingly identical minerals from different ore deposits often exhibit extreme variation in flotation behavior, i.e., that small amounts of analytically undetectable impurities often have a great influence upon flotation

Jan 1, 1969

By Verne C. Fryklund, S. Warren Hobbs

The Coeur d'Alene district in the panhandle of Idaho is one of the major lead-zinc-silver producing areas in the world. The value of recorded production to date has exceeded $2 billion. Country rock comprises six formations of the fine-grained, highly siliceous, and slightly metamorphosed Precambrian Belt Series. Small stocks of monzonitic rocks and several varieties of dikes intrude the sediments. The district is at the intersection of a north trending major anticlinal uplift and the west northwest-trending Lewis and Clark line of which the Osburn fault is the dominant feature. The district structure is complicated and comprises folds, some of which are overturned, and a complex of faults of diverse ages and directions of movement. Late Cretaceous stocks but are also probably Cretaceous in age. The productive veins are localized within a series of 12 subparallel, straight mineral belts that trend approximately N65°W and that appear to be controlled by deep fractures in the basement rocks. The mineral belts are in two groups, separated by 15 miles of post-mineralization movement on the Osburn fault. Veins and ore shoots are variously disposed within each mineral belt. Many crop out at the surface, but others apex several thousand feet beneath it. Local controls that influence the position of ore shoots within the mineral belts include the brittle character of host rock attitude of bedding relative to the mineralized fracture, and the amount and direction of movement on faults. Depth appears to have had little effect on the occurrence or type of ore. Ore occurs in a series of steeply dipping replacement veins of relatively simple mineralogy. Six periods of mineralization, ranging from Precambrian to Tertiary in age, are recognized. The productive galena sphalerite-bearing and tetrahedrite-bearing veins-of the main period of mineralization-are younger than the

Jan 1, 1968

By William B. Plank

AGAIN the records show an unprecedented enrollment of students in the mineral technology schools of the United States and Canada. In the current year, 1938-'39, 9619 students were resident in the 53 schools of the United States arid 1014 in the six schools of Canada. These data are from my fifth study of the mineral technology schools of the United States and Canada. the last previous study having been made for the year 1936-'37. The undertaking as previously was made under the auspices of the Mineral Industry Education Division of the A. I. M. E. The data or, the various schools were collected in the same way as for former studies.

Jan 1, 1939

By C. R. Hayward, H. O. Hofman

The aim of instruction in a metallurgical laboratory is to make real the principles on which metallurgical processes and operations are based, and to foster the spirit of investigation. The materials with which experiments are carried out are ores, metals, and metallic compounds. The method varies with the end sought. A class may work as a whole, each member contributing his share to the solution of a problem, or the students may carry on investigations independently; the former exemplifies class-research; the latter, individual research. It is with a branch of the former, with special reference to ore-treatment, that the present paper deals. In smelting an ore by a well-established process, the result is shown by analyzing the products to see whether their compositions correspond to those calculated in making up the charge; by taking account of stock to show the distribution of metal in the different products made and the losses from dust and volatilization; by casting a thermal balance to find the distribution and losses of heat; and by making a cost-sheet to ascertain, as far as possible, the necessary outlay of money. In lixiviation and amalgamation, the mode of operating has to be varied to adapt a process to the individual ore. Here a number of tests become necessary. Each will consist of a series of experiments with one variable, in order to find the conditions under which the variable gives the best result; a summary of several tests will give the best method of operating. Working a number of charges with the best method will furnish the data desired for ascertaining the recovery of metal,

Jan 1, 1910

By Frederick Prime

The first catalogue of Geological Reports of the United States was prepared by Prof. 0. C. Marsh, and published in the American Journal of Science and Ark for 1567, vol. xliii, second series. Since then the list has more than doubled, and it was thought that the publication of a new catalogue, brought clown to date, would be useful to many of the members of the Institute of Mining Engineers. The compiler will be most thankful to have any omissions or inaccuracies in the list sent to him, to be published as a supplement in the next volume of the Transactions. Especially to have the correct title, number of pages, plates, and maps of any volume on the list to which an * is prefixed, as he has been unable to personally consult such works. A preliminary list was issued last February, which has been almost doubled by the kindness of many friends. The writer desires more especially to express the obligations he is under to the following gentlemen : The Chief of Engineers, U. S. A.; Principal Dawson, Mr. G. M. Dawson, Drs. R. J. Harrington and T. Sterry Hunt, of Montreal; Mr. H. Engelmann, of La Salle, Ill.; Dr. F. V. Hayden and Prof. J. W. Powell, U. S. Department of the Interior; Prof. E. W. Hilgard, University of California; Prof. Henry Y. Hind, Windsor, N. S.; Prof. C. H. Hitchcock, of Dartmouth College; Mr. Henry A. Holmes, State Librarian, Albany; Maj. Jed. Hotchkiss, Staunton, Va.; Prof. W. C. Kerr, Raleigh, N. C.; Dr. J. S. Newberry, of Columbia College ; Prof. W. H. Pettee, of the University of Michigan ; Dr. Samuel H. Scudder, Prof. N. S. Shaler, and Prof. J. D. Whitney, of Harvard College; Mr. Sanderson Smith and Prof'. J. J. Stevenson, of New York; Mr. Addison Van Name, of Yale College, and Lieut. Geo. M. Wheeler, U. S. Engineers.

Jan 1, 1879

By Stanley Herold

A FEW notes on the occurrence and significance of mud volcanoes in Colombia may be of interest at the present time, owing to the renewed activity in geological exploration of, the coastal regions bordering the Caribbean Sea. The best-known volcanoes are found a few miles from the seacoast. One is situated to the south of Puerto Colombia; the second, to the east: of Cartagena near the village of Turbaco; and the third, near the village of Puerto Escondido south of the Sinu River. Others. are reported in more inaccessible localities. Usually they stand 2 1/2 or 3 ft. (0.762 or 0.914 m.) above the surrounding ground at the crater, though several craters from 10 to 20 ft. (3.04 to 6.09 m.,) apart will often build up an extensive mound at low gradient. The shallow mound may cover 1/2 or 3/4 acre (0.2 to 0.3 ha.) with an elevation of 12 or 15 ft. (3.65 or 4.57 m.) at the center. The craters are formed of hardened blue clay; the inside diameters vary from 14 to 24 in. (35.56 to 60.96 cm.). The rim is continuous, except on one side where there is usually a cut 3 or 4 in. deep, thus allowing an overflow. The craters are filled to the rim-cut- with a thick mixture of blue clay mud and water, which is kept in agitation by escaping gas. Fig. 1 shows the bubble in the act of bursting and Fig. 2 the appearance of the surface of the viscous fluid a second or so later. The frequency of the explosions is determined by the weight of the column of fluid in the neck of the volcano, consequently, such explosions are not synchronous in a group of craters. Ordinarily, there are two or three explosions in about 3' minutes. The supply of gas is small but steady and sufficient pressure must accumulate before the bubble can enter the column of fluid. The water is derived from the surface and enters the sedimentary strata not` far distant from the volcano. During long dry seasons, as the supply of water fails the volcano dries and geyser action ceases.

Jan 7, 1919

By R. T. Hukki, P. Voutilainen

This paper describes a new apparatus for continuous wet fine-screening. Its preferred size range seems to be from 0.1 to 1 mm. The supercritical trommel screen is a short cylindrical trommel of wedge-bar type construction operated at a speed greater than the calculated theoretical critical speed and at a speed lower than the speed at which particles introduced into it will centrifuge. The paper describes results obtained with the prototype supercritical trommel screen in pilot plant scale. The results point to a high capacity and simultaneously to a high sharpness of screening. Finally, an analysis is presented of the forces acting in screening on a supercritical trommel screen. In the era of high speed, high capacity processing of raw materials the conventional slowly rotating trommel screen is often considered a relic from the times passed. A typical trommel screen is the cylindrical trommel rotated about a horizontal or slanting axis at a relatively low speed. Its screening characteristics are well known. Trommel screens of various types of construction, methods of operation, performances and other characteristics have been described in detail by Taggart.1 The theoretical critical speed of a trommel screen is defined by the same well known equation as that applied for grinding mills: where ncritical = the numerical value of the theoretical critical speed in rpm, D 1 = the inside diameter of the trommel in feet, and D2 = the inside diameter of the trommel in meters. ncritical corresponds also to the centrifuging speed provided that the coefficient of friction f between the trommel surface and the outer layer of the charge is = 1.0. In a general case: From Eq. 2 it is seen that in all cases where f < 1.0 the centrifuging speed of the trommel is greater than the theoretical critical speed. The supercritical trommel screen concerns screening operations within that speed range which is between the theoretical critical speed defined by Eq. 1 and the centrifuging speed defined by Eq. 2, under conditions such that the coefficient of friction f<1.0. It is reported by Taggartl that the optimum speed of a conventional cylindrical trommel screen 36 in. in diam was experimentally found to be about 16 rpm. From Eq. 1, the critical speed of this trommel is 44.2 tpm. The indicated optimum speed corresponds to (16/44.2) x 100% = 36.2% of the theoretical critical speed. The optimum speed range based on information available seems to vary from 33% up to 45% of the theoretical critical value. The trommel screen operated at a supercritical speed: operates at a speed greater than the calculated theoretical critical speed; operates at a speed lower than the speed at which the charge introduced into it will centrifuge; operates within the supercritical speed range in such a way that the coarse fraction of the charge must slide in respect to the inside surface of the trommel; the outer layer of the said fraction next to the screen tends to proceed in the same direction as any selected point on the trommel surface, but now at a lower speed, and indeed at a subcritical speed; allows to a certain degree adjustment of the maximum determining particle size x of the fine product simply by a variation of the speed of the trommel within the supercritical speed range. With increasing trommel speed, finer and finer material only will get the opportunity to find its way into the fine product while the screen opening remains constant. In conventional practice, the low speed trommel is generally used for sizing of coarse and medium coarse material, but seldom for fine screening. The characteristic feature of the product passed through the conventional trommel is that the determining size x of the biggest particle is barely smaller than the nominal size of screen opening. The supercritical trommel screen, on the other hand, is best suited for sizing of relatively fine material. Furthermore, the characteristic determining size x of the biggest particle in the fine product can be substantially smaller than the nominal width of the screen opening or slot. In the trommel screen best suited for the applications

Jan 1, 1965

By Eugene S. Meieran

The effects of methods of crystal growing, wafer sawing, polishing, routine handling, diffusion, and epitaxial growth on the defects in GaAs are reviewed and studied using reflection and transmission X-ray topographic techniques. In general, it was found that boat-grown crystals exhibited fewer defects than Czochralski crystals, although all crystals showed large numbers of precipitates visible when examined in the electron microscope. Mechanical surface treatments such as sawing and mechanical polishing introduce damage to a depth of about 5 µ, most of which can be removed by suitable chemical or chem-mechanical polishing. In addition, defects can be introduced through routine handling of wafers, for example with metallic tweezers. These defects can be quite severe, and have been observed 20 µ below the wafer surface. Defects can also be introduced through diffusion and epitaxial growth. These defects, which include precipitates, growth pyramids, stacking faults, dislocations, and so forth, can be detrimental to device fabrication. It is shown that wafers or films which appear defect-free optically can contain defects visible in the X-ray topographs. WHILE the use of GaAs in the semiconductor industry has increased very rapidly in the last few years, due mainly to the recent development of many important GaAs devices,1,2 the major limit to the production of commercial quantities of many GaAs devices remains a severe lack of suitable materials technology. This lack is apparent in two critical areas. First, production quantities of high-quality GaAs crystals, reproducibly doped and precipitate-free, simply are not available commercially, although some reasonable quality material is available on a limited first-come, first-serve basis. Second, in comparison to silicon technology, little is known about the effects of processing variables on the defects either present in as-grown GaAs or introduced through processing and handling of wafers. These areas are now receiving some attention from semiconductor device manufacturers, who are studying defects in GaAs in order to better understand how either to prevent their occurrence or to cope with their existence. Most investigations of the defects in GaAs have been made by optical microscopy3-5 or transmission electron microscopy techniques.&apos;-&apos; Recently, however, the imaging techniques of X-ray topography, electron mi-croprobe analysis, and scanning electron microscopy are being applied to the study of GaAs.9-14 In the case of X-ray topography, a one-to-one image is obtained that must be photographically enlarged. In compensa- tion, the defects within entire wafers may be imaged by simple scanning (Lang technique15) if the wafer is reasonably perfect, or by using the scan oscillation technique developed by Schwuttke16 if the wafer is warped or distorted. The purpose of this paper is to both review and extend the general application of X-ray topographic techniques to GaAs. Emphasis will be placed on the effects of growth and process variables on the quality and perfection of both bulk and epitaxial GaAs. Reference to optical or electron microscopy results will be made when useful. Since the effects on defects of a wide variety of processing variables such as crystal growing, sawing, polishing, diffusion, and epitaxial growth will be somewhat superficially reviewed, a fairly extensive bibliography of the most important recent results in these areas is included. However, for completeness, important defects will be illustrated here, although such defects have been previously shown by others. While this paper is concerned with defects rather than with the physics of X-ray scattering, the mechanisms of contrast formation in the topographs will of necessity be briefly mentioned. EXPERIMENTAL GaAs crystals, both boat-grown18 and Czochralski-grown,&apos;8 containing a variety of dopants of various concentrations, were purchased from outside vendors. Wafers were sliced from the crystals using a Hamco ID saw and were mechanically polished using 1 µ diamond paste. Chem-mechanical polishing was done in bromine-methanol as described by Sullivan and Kolb.18 Chemical polishing was done using a modified sulfuric-peroxide solution, 11 parts H2SO4, 1 part 30 pct H2O2, 1 part DI water.5 Zinc diffusion was carried out in a closed tube, using a 10 pct Zn-In source at 825°C for 1 hr. Oxide masking techniques were used to select the area to be diffused. Epitaxial wafers were either purchased or prepared here. All epitaxial runs prepared here were carried out using a Ga-GaAs-AsC13 source in a closed tube at a substrate temperature of 750°C. Wafers were chem-mechanically polished and gas-etched prior to deposition. The X-ray topographs were taken on a Krystallos Lang camera, operating in the transmission scanning geometry (Lang technique15) or in the reflection scanning geometry (modified Berg-Barrett technique20,21). MoKa, radiation was used for all transmission topographs using a Jarrell-Ash 100-µ spot focus. CuKal radiation was used for all reflection topographs using a General Electric CA-7 1-mm spot focus X- ray tube. Topographs were printed from an intermediate contrast inversion film, so the contrast shown in all figures here is the same as that of the original 50-µ-thick emulsion L4 Iiford nuclear plate used to record the topograph.

Jan 1, 1969

By Francis A. Thomson

DO the curricula of our mineral technology schools prepare their graduates to meet properly the full range of their responsibilities in after life? An unequivocal "no" could be returned to this question, because training and experience in professional work are quite as important as adequate college preparation. Furthermore, a had curriculum with a splendid corps of men doing the teaching and a competent body of students doing the learning will produce a better result than an ideal curriculum in the hands of unqualified teachers and poorly prepared students.

Jan 1, 1937

By W. J. Romanow

RECENT papers by Williams, Sherwood, and Boothby,1 Seybolt et al.2 Heikes; and Roberts4 attest to the increasing importance of the hexagonal ferromagnetic compound MnBi. Since the magnetic properties of MnBi crystals are highly anisotropic, it is useful and necessary to have appropriate aids for determining their orientations—a (00.1) standard stereographic projection and a corresponding table of crystallographic angles for this structure. The tables of crystallographic angles for the hexagonal system available in the literature5 are computed for c/a ratios greater than that of MnBi and cannot satisfactorily be used to find the crystallographic angles of MnBi. A table of angles between the crystallographic planes (HK.L) and (hk.1) was calculated for MnBi from the formula0 F=are cos Hh+Kk+ 1/2(Hk+hK) + 3/4 (a/c)2Ll/v(H2 + K2 + HK + 3/4 (a/c)2L2) (h2+ k2+hk + 3/4 (a/c)2l2) on an IBM Type 650 Magnetic Drum Data Processing machine. The lattice constants used are listed in Table I and are those determined by Willis and Rooksby7 at 20°C. More recently published values obtained by both X-ray and neutron diffraction"&apos; show no difference from these significant to the calculation. From the crystallographic angles between the basal plane (00.1) and the general plane (hk.1) in Table I, an (00.1) standard stereographic projection was made for MnBi which is shown in Fig. 1. Acknowledgments The author wishes to thank R. G. Treuting and J. N. Hobstetter for their technical assistance, and Miss D. P. Booth for programing the IBM machine for the calculations. He appreciates the opportunity to read the paper of B. W. Roberts of General Electric Co. prior to its publication. References 1H. J. Williams, R. C. Sherwood, and 0. L. Boothby: Bulletin Amer. Physical Soc., 1956 vol. 1, p. 132. 2 A. U. Seybolt, H. Hangen, B. W. Roberts, and P. Yurcisin: AIME Trans., 1956, vol. 206, p. 605: Journal oF Metals, May 1956. 3R. R. Heikes: Physical Review, 1955, vol. 99, p. 446. .B. W. Roberts: A Neutron Diffraction Study of the Structures of Manganese B.W.Roberts:ANeutronDiffractionBismuthide, Physical. Review, 1956, vol. 104, p. 607. 5 A. Taylor and S. Leber: AIME Trans., 1954, vol. 200, p. 190; JouRNal of Metals February 1954. « C. S. Barrett: Structure of Metals, 2nd Ed., p. 635. McGraw-Hill Book Co. New York and London, 1952. 7B. T. M. Willis and H. P. Rooksby: Proceedings Physical Soc., London, 1954, vol. 67B, p. 290.

Jan 1, 1958

By H. J. Ramey, I. S. Bousaid

Experimental results on the oxidation reaction kinetics in the forward combustion oil recovery process are presented. A total of 48 runs were made wherein a stationary thin layer of coked, unconsoli-dated sand was burned isothermally in a combustion cell. Individual runs were made at various temperature levels to permit determination of the effect of temperature upon the reaction. An expression was obtained for the burning rate of carbon as a function of carbon concentration, combustion temperature and oxygen partial pressure. The carbon burning rate for two types of crude oil indicated a first order reaction with respect to both carbon concentration and oxygen partial pressure. The effect of combustion temperature on the reaction rate constant matched the Arrhenius equation. The activation energy was similar for the two crude oils examined. The activation energy decreased for a porous media containing clay. The rate of oxidation of crude oil at reservoir temperature was found to be significant. Other significant findings included information on hydrogen-carbon content of fuel residues, fuel reactivity and the products of combustion. INTRODUCTION The production of crude oil by underground combustion has been studied in the laboratory by many investigators.1-5 Results of laboratory and field experiments have been reported in the literature describing the forward combustion process. But as yet, no qualitative or quantitative study of the kinetics of fuel combustion involved in this process has been reported. The fuel concentration and the rate at which fuel is burned at the front are important factors governing the air requirement in a forward combustion operation. Although the fuel is essentially unrecoverable crude, the air required to burn the fuel is an important economic factor in this process. Because fuel is burned, the heat transport associated with forward combustion is a key and unique feature of this new oil recovery method. Many investiga-tors5-9 have presented information on the heat transmission and fluid mechanics involved in forward combustion. Berry and Parrish10 demonstrated the utility of considering reaction kinetics in reverse burning. From differential thermal analysis, Tadema11 presented a qualitative discussion of the nature of reactions between oil and oxygen in combustion oil recovery. Although little quantitative work has been done on the reaction kinetics involved in forward combustion oil recovery, an extensive literature does exist on combustion of carbons and oils, and carbonaceous residues from cracking catalyst pellets. Dart, et al., 12 studied the combustion rate for oxidation of carbonaceous residues on clay catalyst pellets, and found the reaction to be second-order with respect to carbon concentration, and first-order with respect to oxygen partial pressure for carbon concentrations less than 2 weight percent of the catalyst weight. The reaction appeared to be first-order with respect to carbon concentration for concentrations greater than 2 percent. Metcalfe13 noted that other workers had found that aging of the fuel during the combustion process was responsible for changing coke properties, and it accounted for the apparent second-order carbon concentration effect found by Dart, et al. It appears that burning of residues from cracking pellets is first-order with respect to both carbon concentration and oxygen partial pressure. Dart, et al., also observed that hydrogen in the hydrocarbon residue appeared to react faster than the carbon. Lewis, et al.,14 studied oxidation of charcoal, coke and graphite in a fluidized bed. Gas velocities were high enough to partially lift and circulate the carbon particles. Their results indicated first-order reaction dependency with respect to both carbon concentration and oxygen partial pressure. One

Jan 1, 1969

By J. E. 214-000-000-010 Warren, M. R. J. Wyllie, T. Meidav, L. Scharon, R. Uhley, A. J. deWitte

By considering the stoichiometry of the underground combustion process, an equrztion was derived relating the point velocity of the combustion front as a function of the air flux, fuel content, efficiency&apos; of oxygen uitilization, hydrogen:carbon ratio, and ratio of carbon dioxide In carbon monoxide produced. In addition, an equation for cnlcrllating the amount of injected air necessary 10 produce the oil from I Cu. ft of reservoir space was derived. This equation has a direct bearing on evaluating compression costs for the process. Values calculated from these equations are in good agreement with experimentnlly obscrvcd values obtained from laborator) tube runs reported in the literature. The equations are also u\eful for atlcrlyzinf: experinlental data for inconsistencie.r.. I NTRODUCTION The injection of energy in the form of heat into an oil-bearing formation as a means of increasing the recovery of oil has been the subject of much discussion and experimentation as far back as 1920. The ideas have ranged from the injection of steam to the direct use of electricity as a means of getting thermal energy into a formation. However, most laboratory and field studies have been confined to the process whereby a portion of the crude in the reservoir is burned to generate the necessary heat to increase the mobility of the oil by reducing its viscosity. A recent paper by W. L. Martin, et al.&apos;, described the results of a number of laboratory experiments in which the combustion process was studied in a sandpack. Studies such as this indicate that with the temperatures involved, the oil is partially coked in this process and it is this coke which provides the fuel for combustion. The combustion of this residual coke can be analyzed theoretically by applying simple stoich-iometric principles to the combustion process. It is the purpose of this paper to compare the results reported in these experiments with those obtained from theoretical considerations. The variables studied by Martin, et al, among others, include combustion front velocity, air flux, oxygen utilization, fuel concentration, ratio of carbon dioxide and carbon monoxide in combustion gases, and the hydrogen:carbon ratio of the residual fuel. All these variables come into consideration when the stoichiometry of the combustion process is studied. The experimental conditions and results are tabulated in Tables 3 and 4 of Ref. 1. For purposes of comparison with calculated results, it was necessary to change the units of a number of the variables. UNDERGROUND COMBUSTION STOICHIOMETRY The combustion or oxidation of the carbonaceous residue or "coke" on the sand can be described in terms of the equation: where n is atomic ratio of hydrogen to carbon, m is ratio of moles of CO2 to CO produced, and CH. is taken as the unit molecular weight, realizing that actually the coke has a large range of high molecular weights. Assuming that all the fuel laid down in the sand is burned, the ratio of moles of oxygen consumed to moles of coke can be written as follows. Moles 0MolesMolescoke In terms of moles O2 per pound of coke, where 12 + n is the molecular weight in pounds per mole. If the 0, consumed is measured in standard cubic feet (60°F and 1 atm) and the coke in pounds per cubic foot of formation, 2, then:

By Roland de Wit

Conclusions reached in a paper by weertmanl are amplified in a mathematical and graphical way. It is shown that in a stressed crystal a straight dis-location may be in a position of unstable equilibrium with respect to helix development, and how a small perturbation may start the dislocation off on its helical path. Helix development occurs by diffision; bulk diffusion is necessary for development from a screw, but core diffision is sufficient for development from an edge dislocation. For a mixed dislocation helix development can take place by core diffusion if the helix also climbs; a diffusion reversal takes place when the slope of the helix equals the slope of the Burgers vector. The work done on a crystal by the external forces is graphically shown to be consistent with the direction of motion of the dislocation in helix development. Finally a detailed mechanism for tangle formation from helices is presented. In the course of helix development a glide situation may be reached where a segment of each helix loop lies in a slip plane in which it can expand by glide. Thus is it visualized how a helix can deteriorate into a tangle. A paper by weertmanl proposes dislocation-tangle formation by a helical dislocation mechanism. The present paper amplifies Weertman&apos;s arguments in a mathematical and graphical way and presents some further ramifications of the proposed model. The importance of dislocation tangles is discussed in Weertman&apos;s paper and the references cited therein. The mechanism of their formation is not yet understood. Weertman proposes that in cold-worked crystals conditions exist suitable for the conversion of straight dislocations into helices and subsequently into tangles. Helix formation occurs by a diffusion process and Weertman proposes that at low temperatures only core diffusion is important. The present paper necessarily repeats some of Weertman&apos;s work. Since the mathematical development and notation used are slightly different from his, this was thought necessary for clarity. GEOMETRY OF THE HELIX weertman2 has shown that the equilibrium form of any dislocation line is a helix if it is assumed that the energy per unit length (line tension) of the dis- location is constant. For the special case that no external forces act on the dislocation, the helix reduces to a straight line. We shall assume in this paper that the dislocation has a helical form even when it is not in equilibrium. The parametric equation of a helix is, see Fig. l: where a is the radius of the cylinder tangent to the helix, and 270 the pitch of the helix. The pitch is related to v, the number of turns per unit length (along the axis) by the relation: When a = 0 Eq. [I] gives a straight line in the z direction. The growth of a straight dislocation into a helix is now described mathematically by letting a vary from zero to its final value. The tangent to the helix is given by where is the path length along the helix. This gives the direction of t and since its magnitude is unity we must have So that dcp/ds = (a2 +p2)-"&apos;. The curvature of the helix is given by where n = -(cos + sin) is a unit vector normal to the helix. Note that the vectors k and n always point toward the axis of the helix, Fig. 1. FORCE ON THE HELIX The external force which makes the straight dis-

Jan 1, 1963

Allan Gibb, Mount Perry, Queensland, Australia (communication to the Secretary):—In drawing conclusions from his observations, Mr. Van Liew has apparently overlooked the reduction in weight that takes place in the content of the converter. The percentage-compositions of the matte, etc., are not directly comparable for determining the rate of elimination of the impurities; and, in the absence of exact weights (which in such an operation could not be obtained), it is necessary to determine the relation between the impurities and the copper with which they are combined at various stages, in order to get data that are comparable. Owing to a portion of the copper being removed in the slag, etc., the weight of copper in the converter is not a fixed quantity, but.it is sufficiently approximate to permit very reasonable comparison. The analytical data given by Mr. Van Liew, reduced to this basis (a ratio between the impurities and the copper with which they are combined), are shown in the table on page 958. From this table it will be evident that Mr. Van Liea&apos;s conclusions as to the source of heat at digerent stages are not quite correct. During the first 10 minutes, no iron is scorified, the heat being derived from the oxidation of the sulphur, of which 7 per cent. of the total is removed in this time. Prom

Jan 1, 1904