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By Burt C. Mariacher

To note that environmental considerations had a major im¬pact on the minerals processing industry in 1971 would be something less than a profound observation. The degree of its importance was demonstrated by MBD when it established the Environmental Committee as a new unit committee within the Division to achieve greater participation in exchange of information relating to the technologies and problems involved. It is appropriate and necessary to devote special attention to this timely aspect of minerals processing, as its influence penetrates the research, engineering and operations of almost all unit technologies that comprise minerals processing. The pollution abatement aspect of this industry has been such a dominant factor in recent years there is reason to wonder whether progress in unrelated technologies has been curtailed. Perhaps so, to some degree, but unit committee reviews presented in this article suggest rather that it would appear to have served as a catalyst for accelerated progress in development of new methods and improvement in more conventional ones. Present concepts regarding primary metal or mineral recovery and by-product potential may change considerably as a result of improved technology in waste product treatment.

Jan 2, 1972

By Stuart Croasdale

NOT long ago I was called upon to conduct some experiments on the treatment of ores from the New Cornelia copper mine, Ajo mountains, Arizona, for the Calumet & Arizona Copper Co. The problem was a very interesting one and contained some unusual features. Incidental with this problem was the utilization of a large amount of low-grade pyrite in the Bisbee mines of the company, provided this could be accomplished by any feasible method. The New Cornelia mine is situated 45 miles south of Gila Bend, the nearest railroad point, on the Southern Pacific Railroad. It is about 160 miles, almost due west, from Tucson. This section is one of the most arid in the United States. The normal annual precipitation, as given by the United States Weather Bureau covering a period from 1870 to 1901, is 3 to 5 in. During June and July, 1913, the records kept by the company gave the following results. These are all I have available, but they show the enormous evaporation that can be expected, which may be a factor in leaching operations on a large scale.

Jan 8, 1914

By W. A. Forbes

PAGE Introductory............357 ReasoNs for Gas Cleaning.........358 First Methods of Separation of Dust.......359 Amount of Dust Produced by the Blast Furnaces of the United States Steel Corporation During 1912.....359 Dust Content in Blast-Furnace Gas.......360 Primary Cleaning. Dry Cleaning: General Remarks..........360 Braasert- Witting Whirler........362 Brassert Modifications of Brassert-Witting Whirler....363 Dyblie Whirler..........363 Remarks on Efficiency of Dry Cleaning......366 Wet Cleaning: Zschocke System..........367 Duquesne Tower..........367 Bian Gas Washer..........369 Final Cleaning. Wet Cleaning: Theisen Gas Washer.........371 Theisen Disintegrator Gas Washer.......372 Schwerz-Bayer Disintegrator Gas Washer..... 374 Fowler & Medley Vertical Gas Washer......376 Feld Gas Washer..........377 Reco Centrifugal Gas Washer........379 Sepulchre Gas Washer.........381 Dry Cleaning: Halberger-Beth Gas-Cleaning System......382 Smith.Bagley Gas-Cleaning System,......384 Howard Dust Separator.........387 Possible Separation of Dust by Electrical Precipitation ... 389 KapnOGraph............389 Methods of Determining DUst in Gas.......389 Advantages of Clean Gas.........393 Introductory. During the early stages of blast-furnace practice. the gas formed in the furnaces by the combustion of the coke used in smelting the ores was allowed to escape into the atmosphere. The light furnished

Jan 1, 1914

By H. A. Meyerhoff, R. J. Colony

Deposits of iron are widely scattered in the folded Cretaceous rocks and the associated igneous intrusives of Puerto Rico. Most of them are too small for commercial development, but a few have aroused some scientific and economic interest, among them the large body of residual limonite at the west end of the island near Mayagüezl-6 (Fig. 1) and the mixed hematite and magnetite deposit on the southern slopes of the Sierra de Cayey, about four miles north of Arroyo.7"9 Neither of these orebodies has been developed, nor have investigations of the widely distributed deposits of magnetite, which include all the remaining occurrences of iron deserving of economic consideration, proceeded beyond the exploratory stage. With the possible exception of the mixed deposit near Arroyo, the magnetite is directly associated with andesitic and dioritic intrusives, which invade the Cretaceous rock section, and the bulk of it, occurring in calcareous sediments, is clearly of contact-replacement origin. The small deposit on Rio Portugües, north of Ponce, is found in a limestone band near its contact with an andesite dike.10,11 Two deposits of unde-

Jan 1, 1935

By H. A. Meyerhoff, R. J. Colony

Deposits of iron are widely scattered in the folded Cretaceous rocks and the associated igneous intrusives of Puerto Rico. Most of them are too small for commercial development, but a few have aroused some scientific and economic interest, among them the large body of residual limonite at the west end of the island near Mayagüezl-6 (Fig. 1) and the mixed hematite and magnetite deposit on the southern slopes of the Sierra de Cayey, about four miles north of Arroyo.7"9 Neither of these orebodies has been developed, nor have investigations of the widely distributed deposits of magnetite, which include all the remaining occurrences of iron deserving of economic consideration, proceeded beyond the exploratory stage. With the possible exception of the mixed deposit near Arroyo, the magnetite is directly associated with andesitic and dioritic intrusives, which invade the Cretaceous rock section, and the bulk of it, occurring in calcareous sediments, is clearly of contact-replacement origin. The small deposit on Rio Portugües, north of Ponce, is found in a limestone band near its contact with an andesite dike.10,11 Two deposits of unde-

Jan 1, 1935

By Herbert Clark Hoover, Lou Henry Hoover

DIGGING of veins I have written of, and the timbering of shafts, tunnels, drifts, and other excavations, and the art of surveying. I will now speak first of all, of the iron tools with which veins and rocks are broken, then of the buckets into which the lumps of earth, rock, metal, and other excavated materials are thrown, in order that they may be drawn, conveyed, or carried out. Also, I will speak of the water vessels and drains, then of the machines of different kinds,1 and lastly of the maladies of miners. And while all these matters are being described accurately, many methods of work will be explained. There are certain iron tools which the miners designate by names of their own, and besides these, there are wedges, iron blocks, iron plates, hammers, crowbars, pikes, picks, hoes, and shovels. Of those which are especially referred to as " iron tools " there are four varieties, which are different from one another in length or thickness, but not in shape, for the upper end of all of them is broad and square, so that it can be struck by the

Jan 1, 1950

By Alden Greninger

METALLURGISTS have long believed that martensite in steel forms as plates along the octahedral {111} planes of austenite. Much has been written about mechanisms whereby units of the austenite lattice are pictured as transforming to martensite by shearing movements initiated along the octahedral planes of austenite, supposedly resulting in plates of martensite lying parallel to these planes of shear. A critical inspection of two or three photomicrographs of quenched hypereutectoid steel led us to the conclusion that the orientation habit of martensite, at least in hypereutectoid austenite, could not possibly be octahedral. Inasmuch as recent studies30,31 of the martensite-type reaction in nonferrous alloy systems have established the irrational orientation habit as characteristic of this type of lattice transformation, the need for a thorough restudy of the crystallography of martensite formation in steel was evident. The present paper reports the results of such a study, extended to include both cementite and some of the products of constant-temperature decomposition of austenite. Also reported are a few of the results obtained from a microscopic and X-ray study of the austempering process in very high-carbon steel.

Jan 1, 1940

By Wilbur T. Stuart

TO assist the mining industry in attacking problems of water control, the U. S. Geological Survey has begun a program of research in mining hydrology. In certain fundamental respects water control is similar to development of water supplies from wells or to the drainage of agricultural lands, as many of the tools developed in recent years for quantitative ground-water problems are applicable, with modification, to mine-water problems. In 1952 a 30-day pumping test conducted jointly by the Eureka Corp. Ltd. and the Defense Minerals Exploration Agency provided an opportunity to gain knowledge concerning water movements around a flooded mine shaft. The methods of analyzing the data may be used as a guide for the evaluation of similar problems elsewhere. The Fad shaft of the Eureka Corp. is on Ruby Hill, 1 1/2 miles west of Eureka, Nev. The shaft was completed at a depth of 2465 ft in November 1947 at a site adjacent to the downfaulted block in which the ore was found. As the drift on the 2250 level progressed toward the ore zone, a large flow of water was encountered after the Martin fault was intersected. This flow exceeded the installed pump capacity, and an unsuccessful attempt to recover the shaft and the 2250 level was made in 1948.1, 2 Geology and Hydrology: The complex structure of Ruby Hill is that of an anticline broken first by thrust faulting and later by normal faults. The present orebody comprises several mineralized zones within a block of the Eldorado limestone of middle Cambrian age which was downfaulted 1400 to 1600 ft, and it may be related to a similar body mined at a higher level south of the Ruby Hill fault. At the depth of the largest zone of ore the block is roughly rectangular in shape, about 1000 ft wide and 1500 ft long, and dips about 30" NE, see Fig. 1. It is apparently bounded on the south by the Ruby Hill fault, on the east by the Jackson fault, on the north by the Martin fault, and the west by the Bowman fault. Within the block, but between the Ruby Hill and the Martin faults, are the Office and Adams Hills faults; west of the block and the Bowman fault are the Albion and Spring Valley faults. There are many conflicting reports concerning the water-yielding characteristics of the Eldorado limestone and the condition of the fault zones, that is, whether they are open or tight. However, the diamond-drill records indicate that open spaces as much as 2 or 3 ft across were encountered, and considerable cementing and lining of holes was necessary to maintain circulation of drilling fluid. There is also evidence that the Eldorado limestone was cavernous where it was mined in the early days south of the Ruby Hill fault. At the site of the Fad shaft the formations encountered from the surface down included the Pogonip limestone, Dunderberg shale, Hamburg limestone, and Secret Canyon shale. These formations did not yield large quantities of water to the shaft. The Pogonip limestone, which appears to be permeable and might yield water elsewhere, is above the water table in the vicinity of the shaft. The Secret Canyon shale, immediately overlying the Eldorado in some places but in most places separated from it by the Geddes limestone,3 is apparently tight and does not transmit water. During the 30-day test period the shale briefly confined the water in the underlying formations so that artesian conditions were observed in drillholes E and F, which are cased into the Eldorado limestone, whereas unconfined conditions were observed in drillholes B, C, and D, which were open to the shale. The Geddes limestone, which normally lies between the Secret Canyon shale and the Eldorado limestone, was not encountered in the Fad shaft. The Geddes, a flaggy, fractured limestone, is reported capable of yielding large volumes of water. Water stored in the interstices of this thin-bedded limestone within the Ruby Hill fault zone on the 1200 level of the Locan shaft drowned the pumps in 1923 when the Richmond-Eureka Mining Co. attempted to explore the area along the fault. Eldorado limestone was not encountered in the Fad shaft. In the ore-block area the Eldorado limestone was not entirely offset from other water-yielding formations by movement along the Bowman fault; therefore it may be hydraulically connected with the other formations. Adjacent to the Ruby Hill, Jackson, and Martin faults, the Eldorado lies in contact with other possible water-yielding formations. One of these, the Prospect Mountain quartzite, is separated from the Eldorado by thin, sheared, and broken beds of the Geddes within the Ruby Hill fault zone. A limited examination by the author of the Prospect Mountain quartzite in the Richmond mine at a higher level and south of the Ruby Hill fault indicates that the quartzite is poorly permeable. The monzonite mass south of the quartzite would be a further barrier to the flow of water. The poor permeability of this area is substantiated by records of levels at which water was encountered south of the Ruby Hill fault. In view of the normally low rate of ground-water recharge, if this desert area had been permeable, water levels could not have been maintained at altitudes of many hundred feet above the present water table west and north of Ruby Hill. Thus the ore-bearing block of Eldorado limestone is in contact with possible water-yielding rocks on at least two sides, and if the fault zones are possible conduits for water circulation the geologic and hydrologic conditions are suitable for the infinite-aquifer type of analysis as used and modified here. History of Pumping: During sinking of the Fad shaft a maximum pumping rate of 1500 gpm kept the shaft dewatered sufficiently, but in March 1948, after the 2250 level drift passed through the Martin fault into the Eldorado limestone, the pumps and shaft were flooded. Subsequently additional pump-

Jan 1, 1956

By J. Winlock

To have been chosen by you to give the Howe Memorial Lecture is the greatest honor I have ever had and I should like to have you know that I appreciate it deeply. Many years ago I had the privilege and the pleasure of working with Professor Howe in the private laboratory which he had established in his home at Bedford Hills, New York. Without doubt he was one of the world's greatest metallurgists and so you can imagine what a difficult task it has been for me to live up to his teachings. Every morning Professor Howe would outline the work he wanted done and the recollections of those conferences are clear to me to this day. Sometimes he would ask me to ride in his automobile and the chauffeur had full instructions to go no more than fifteen miles an hour. If he did so, Professor Howe was sure to rap upon the man's shoulder with his cane. I assure you, however, Professor Howe's thinking was not at that rate. His homely advice, his patience and his perfect control of the English language still impress me. Many times I heard him dictate a complicated paper on metallurgy and never find it necessary to change a single word. There are no better words to describe the character of Professor Howe, in my opinion, than those used by Professor Sauveur when he presented the John Fritz Medal to him in 1917: "Lover of justice and humanity Public servant and public benefactor, Master of the English Language, Loyal and devoted friend, Untiring and unselfish worker in an important field of science." I hope you will bear with me with the same patience and understanding which he used to give to me. The peculiar behavior of steel at the yield point has long been known and has been the subject of much research, both in this country and abroad.',' Many theories, including some of mine and my colleagues, have been suggested, but none of them, in our opinion, fully explains to our satisfaction why the phenomena occur. Of particular importance has been the work of Nadai,3 Siebel and Pomp,' Sachs and Fiek,5 Rawdon,0 Kenyon and Burns,' Gensamer," Gensamer and Meh1,0 Davenport and Bain,'" Fell," Deutler,12 Brinkman,13 MacGregor,14 Hollomon,15 Cot-trell,16 and Palm." The question of what is occurring during this singular behavior is not only of interest from an academic point of view, but is of great practical importance for at least two reasons: 1—The highly localized plastic flow which occurs during the deep drawing of light-gage steel gives rise to surface markings which seriously mar its appearance, Fig. 1. If the forces causing the deformation are primarily tensile forces, these surface markings occur as depressions in the surface. Whereas, if the forces causing the deformation are primarily compressive, irregular lines of elevations occur. These surface markings are known as Luder's lines, Hartmann lines, the Piobert affect, and, in the shop, as "stretcher strains." 2—The steel is in the most suitable condition for deep drawing after the yield point phenomena have been removed. When this is done, the steel may be deep drawn more easily and to a greater extent.' It should be mentioned that steel is not the only metal which shows this peculiar behavior at the yield point. Stretcher strains occur, also, during the deformation of some copper-nickel-zinc alloys." The purpose of this paper is not an attempt to describe what causes the steel to behave in this peculiar manner, but an attempt: l—to describe what is taking place at the yield point; and 2—to show the influence of the rate of deformation on the tensile properties of some plain carbon steels. As is well-known, there are two methods of deforming a metal in tension: 1—by actually hanging an increasing amount of dead weight on the metal; or 2—by deforming the metal at some given rate or rates by means of oil pressure cylinders, screws, etc. With the first method, the load is always present and, clearly, no drop in load can ever occur while the steel is deforming. With the second method, the registered load is the resistance of the steel to the deformation being imposed upon it. The second method is the one most widely used, and is the one referred to throughout this paper. In order to describe clearly what is occurring at the yield point in steel, it will help, I believe, if a description is first given of what occurs when alumi-

Jan 1, 1954

By E. J. Roberts

Prior to 1916, thickening was an art, and any accurate decision as to what size of machine to install to handle a given tonnage of a specific ore must have been one of those intuitive conclusions, based on both intimate and extensive acquaintance with thick-ners and ore pulps. Then in 1916 "knowledge of acquaintance," became "knowledge about" with the publication of the Coe and Clevenger paper.' The unit operation of thickening had graduated to the status of an engineering science. The fundamental similitude relationships for the two major phases of the operation were defined so clearly that batch tests on models as small as liter cylinders could serve to specify protypes as large as 325 ft in diameter. It is quite apparent from reading the literature that Coe and Clevenger's contribution is not generally appreciated. In so far as the basic engineering relationships are concerned, the only real advance which has occurred in the 30 odd years which have elapsed since the Coe and Clevenger paper is the recognition of the effect of the rakes on the thickening process. Bull and Darby2 noted this in 1926, and the extensive use of the "gluten type" thickener, in which the effect is magni-fied, bears witness to its importance. Comings3 further verified this effect of the rakes. As a matter of fact, a number of papers show an apparent regression from the Coe paper in that the area determinations are made on the basis of a single test from One concentration of solids. Coe and Clevenger amply demonstrated that this is unsafe, since the controlling zone may be one other than that of the feed dilution. Comings3 neatly demonstrated this without apparently realizing it. Of course there have been significant advances in the application of the operation to industry. Open tray thickeners were introduced to save area; balanced tray thickeners, washing thickeners, and multifeed clarifiers were developed with all of their special hydraulic and mechanical problems. Combinations of all kinds have been introduced, such as combination agitators and thickeners, combination flocculators and clarifiers, combination thickeners and filters. With the establishment of the operation on a firm engineering foundation, installation was facilitated and expansion proceeded. There are still problems, of course, functional as well as mechanical. Sometimes the moisture in the underflow obtained in practice is not as low as is expected on the basis of the test data. Sometimes the underflow is so "thick " that its discharge and subsequent handling requires special attention. Island formation plagues some operators. The use of the thickener as a surge basin and blending tank in the cement industry poses unusual problems. Design of rakes and the drive mechanism must be continually im-proved. Corrosion problems must he overcome. Power requirements for raking the settled solids occasionally is the controlling factor as it was in the case of the all American Canal desilting installation. Other similitude relationships and design problems come into the picture when we enter the field of clarification or nonline settlement. We have an energy dissipation problem in introducing the feed and any models must satisfy the Froude model relationships. Autoflocculation requires detention which involves the same similitude laws that we encounter in the compression zone. Approach to an Exact Science The next step beyond having control of the similitude relationships is to understand the why of these relationships right back up the line to first principles. The ultimate might be that, if given the mineralogical composition of the solids and their size distribution together with an analysis of the suspending liquid, we could calculate the entire thickening behavior of the system. Then we could say we had reduced the operation to an exact science. True it might be more trouble getting this basic analytical data than to make our empirical determinations for area and volume, and we would need an ENIAC to calculate the results, but that does not detract from the desirability of such understanding. Considerable work has been done by the chemical engineers with this end in view. Comings,3 Egolf,4 Work,5 Kam-mermeyer,6 Steinour,7 and others have studied the problem. The writer has no final answer to the thickening story but would like to propose a picture of the mechanics of the two phases of thickening which has been found useful in understanding the subject and which leads to some convenient relationship in treating the compression step and arriving at the compression depth.

Jan 1, 1950

By C. S. Barrett, A. Smigelskas

There have been no publications of the deformation and recrystallization orientations of the metal beryllium, yet pronounced textures would certainly be anticipated since it is close-packed hexagonal in structure. Having an axial ratio approximately that of magnesium, beryllium probably deforms by nearly the same slip and twinning mechanisms that operate in magnesium, and the textures are likely to be similar or but slightly different from the magnesium textures. In the tests reported below this is found to be the case; the textures are found to differ from those of magnesium only in the details of the scatter from the average orientation. This report covers not only samples rolled at room temperature, but some rolled at elevated temperatures. Since magnesium has been suspected by some investigators of altering its crystallo-graphic deformation mechanism at elevated temperatures, it was considered possible that beryllium might do so and alter its textures accordingly. No pronounced alterations were found, however. Unfortunately, the theory of deformation textures is not in a state of development that permits one to deduce the deformation mechanism from a knowledge of the textures, which means that the similarity of textures at different rolling temperatures, reported here, cannot be taken as definite evidence that the deformation mechanism is actually the same at all temperatures. The general similarity of the deformation textures of magnesium and beryllium also extend to the recrystallization textures of the two metals, judging by the pole figures for recrystallized sheet presented in this report. Samples were prepared in the form of composite sheets made up of small pieces stacked in a pile. Each piece was trimmed with scissors so that an edge was parallel to the rolling direction, dipped in paraffin, and assembled into the pack by aligning it under the cross hair of a microscope. As the desired orientation was obtained on each piece it was secured in place by touching with a hot wire to melt the paraffin. A stack of ten or fifteen pieces was built up in this way, then trimmed to the shape of a T; the portion to be X rayed was then etched to the shape of a wire about 0.045 in. diam with 6N HCl. This method of shaping the sample is a modification of that used by Bakarian on magnesium.' The absorption of the rays in the sample was so slight that it caused no difficulty in interpreting the films. Exposures were made with a 0.030 in. diam pinhole, using molybdenum radiation (40 kv, 25 ma, Type A film at 5 cm, 2 to 3 hr exposures). With the recrystallized specimens it was found necessary to oscillate the specimen so as to reduce the spottiness of the lines. A range of oscillation of 5" was SUB- cient to produce reasonably satisfactory patterns, though the quality was somewhat inferior to that of the deformation texture patterns, and only two degrees of intensity were read from the arcs on the films. Typical photo-grams for each of the deformation textures and the recrystallization texture are assembled in Fig 1. The pole figures were plotted in the usual way with the intensity of the various portions of the diffraction rings estimated by eye. Seven to nine films were made of each sample and each was carefully read in plotting the pole figures. Typical series included exposures with the beam normal to the rolling direction and at 11, 26, 41, 56 and 71" to the cross direction, plus two exposures with the beam normal to the cross direction, and at 11 and 79" respectively to the rolling direction. The rolling was in each case considered sufficient to develop the final texture: the reduction by cold rolling was 84 pct (from 0.0045 to 0.0007 in. thickness), following prior hot rolling in longitudinal and transverse directions and recrystallization; the reduction by hot rolling at 800°C was 90 pct (0.010 to 0.001 in.), following similar prior treatment; the reduction by rolling at 350°C was 88 pct (from 0.005 to 0.0006 in.) after similar prior treatment. The recrystallization texture was determined on a sample rolled at 350" to a reduction of 88 pct (0.0165 to 0.002 in.) after similar prior treatment, then mounted between steel strips to keep it flat and annealed at 700" in an atmosphere of argon. Discussion of Results The results of the X ray determinations are assembled in the pole figures of Fig 2, 3, 4 and 5 for rolling at

Jan 1, 1950

By John L. Miles

John L. Miles (Arthur D. Little, 1nc.)—Pollack and orris" have reported measurements on electron tunneling through A1-A12O3-A1 sandwiches in which the oxide was formed by gaseous oxidation in a glow discharge. From these measurements they deduced the asymmetry of the barrier and, since this is small, conclude that the mechanism suggested by Mott19 for the growth of oxide in thin A12O3 films is inapplicable. In earlier papers20 Pollack and Morris report similar work for oxide films grown thermally. In this case they find a greater asymmetry and conclude that the Mott mechanism is valid. I would like to point out that both these conclusions are quite unjustified. Mott suggests that the growth of the oxide film on aluminum results from the passage of ions through the already present film of oxide under the action of an electric field. This field results from a constant voltage which is in effect a contact potential between metal on one side of the barrier and adsorbed oxygen ions on the other side of the barrier. The theory does not require that the oxide grown is nonuniform either in stoichiometry or structure. It does however specifically assume that the partial layer of ionized oxygen on the surface remains adsorbed on the surface of the growing oxide. In other words, the so-called "built-in field" remains in the oxide only as long as the ionized oxygen is present. When a counter electrode of aluminum is deposited on the oxide, it will react with the adsorbed oxygen on the surface of the oxide, thus forming a small additional amount of oxide. It is clear, then, that there is no requirement in the Mott theory of oxide growth which would necessitate tunneling currents through an Al-A1203-A1 sample to be different when the polarity is reversed. Neither does the theory eliminate the possibility that some additional mechanism could cause the tunneling barrier to be asymmetric and hence tunneling currents to be a function of polarity in such a sandwich. Thus these tunneling-currents measurements are not germane to the question of whether the Mott mechanism is the true method of growth of aluminum oxide films. In fact, it is not surprising that there should be a difference between the oxide properties at the two interfaces (with resulting asymmetry in the tunneling barrier) since the growth conditions and growth rates must have been quite different at these two positions. S. R. Pollack and C. E. Morris (authors' reply)— The point raised by Miles above is one has caused some confusion in the past. The following is an attempt to clarify this point. The built-in field which is responsible for the growth of the thermal oxide at low temperatures arises, according to Mott, because of the passage of electrons from the Fermi surface of the oxidizing metal to surface states introduced by the adsorbed oxygen. It is assumed that the energy of these surface states lies below the Fermi energy of the metal. Electrons therefore continue to flow from the metal to the surface until the built-in electric field raises the potential energy of the surface states to the value of the Fermi energy in the metal, at which time equilibrium is obtained between the surface states and the metal. That is in equilibrium as many excess electrons pass from the metal to the surface per unit time as vice versa. The surface of the oxide prior to deposition of a metallic counterelectrode can then be pictured as follows. The Fermi energy lies in the energy gap of the oxide and is essentially pinned at the energy of the oxygen surface states. The vacuum work function of the oxide is then given by the sum of the electron affinity of the oxide (i.e., the difference in energy between the vacuum and the conduction-band minimum) plus the energy difference between the conduction-band minimum and the Fermi energy. The deposition of a metal onto the surface of the oxide can result in a transfer of electrons across the extremely thin oxide only if there is a contact potential difference between the deposited metal and the parent metal or oxide. That is if the vacuum work function of the deposited metal differs from that of the parent metal, then charge can be redistributed across the oxide in order to equilibriate the Fermi energy across the structure. (It should be

Jan 1, 1965

By C. G. Dunn, J. L. Walter

Secondary recrystallization to the (110) [001] texture in high-purity silicon iron occurs if low-oxygen material is annealed in a nonoxidizing atmosphere. Any departure from these conditions results in a growth of (100) oriented grains. The nature of the matrix and secondary recrystallization structures and textures and the nature of grain boundary interactions during growth show that the low gas-metal interfacial energy of the (110) surfaces provides the driving force for growth of these grains. A type of grain growth, characterized by a driving force which derives from energy differences of {hkl} surfaces at the gas-metal interface, has been treated in recent papers.&apos;-7 Secondary recrystallization to the cube text!:: in high-purity silicon iron provides one example. The present paper also deals with a surface energy driving force but the texture that results by secondary recrystallization is not the cube texture; it is a texture in which the (110) plane is in the plane of rolling and the [001] direction is in the direction of rolling. The phenomenon described in this paper is different from the impurity (dispersed phase)-controlled secondary recrystallization process in which the (110) [001] oriented grains grow under the action of grain boundary driving forces.8-12 It is also different from tertiary recrystallization,2 which also produces the (110) [001] texture in high-purity silicon iron, since the matrix textures and grain sizes are different. Finally, it is unlike any other form of secondary recrystallization reported in the literature. The possibility of obtaining the (110) [001] texture in high-purity silicon iron became clear in a study of the effect of impurity atoms on the energy relationships of (100) and (110) surfaces. In this study Walter and Dunn6 observed the migration of (100)/(110) boundaries, i.e., boundaries between two grains, one of which has a (100) plane and the other a (110) plane, respectively, parallel to the plane of the sheet specimen. At 1200°C the (100)/(110) boundaries advanced into (100) grains in a vacuum anneal, then reversed their direction and migrated into (110) grains in a subsequent anneal in impure argon. Finally, the direction of migration reversed once again with (110) grains growing into (100) grains in a second vacuum anneal. These results were explained in terms of a change in concentration of oxygen atoms at the gas-metal interface during the anneals. Thus, oxygen atoms were added to the surface during the anneals in impure argon to the point where ?100, the specific surface energy of the (100) oriented grains, was lower than ?110, the surface energy of (110) oriented grains. In vacuum, however, the oxygen concentration at the surface was lowered to the point where ?110 < ?100. Concerning the possibility of secondary recrystallization in high-purity silicon iron with a low initial oxygen concentration, the observed effect of adsorbed oxygen atoms has indicated6 that a good vacuum anneal would favor the rapid growth of matrix grains with the (110) plane in the plane of the sheet much more than grains in the (100) orientation. The growth of only (110) oriented grains of course would depend upon y110 being less than ?hkl, where hkl refers to any plane different from (110). The present paper is concerned with the application of the above ideas to secondary recrystallization to the (110) [001] texture in high-purity silicon iron. The matrix and secondary recrystallization textures and structures are defined and discussed. Observations of growth of nuclei for secondary recrystallization and of boundary interactions are included to provide direct information on the surface energy relationships between (110) and other (hkl) surfaces. EXPERIMENTAL PROCEDURE As before, 2,4-6 high-purity iron and silicon were melted and cast in vacuum to provide an alloy containing 3 pct Si with less than 0.005 wt pct impurities. The oxygen content of the ingot was lower than in previous ingots, being approximately 3 ppm (by weight). The carbon content of this ingot may have been slightly higher than was found for previous ingots. The same rolling and annealing schedule used previously2 was followed in this study to obtain samples 0.012 in. (0.3 mm) thick. These samples were electropolished prior to annealing. After rolling and polishing, the oxygen content of the material was approximately 6 ppm; material used in the previous studies contained about twice this amount of oxygen.

Jan 1, 1961

By J. E. Graham, A. H. Glenn

Oil operators engaged in drilling on the Continental Shelf of Louisiana and Texas are in agreement that adverse weather and wave action are two of the greatest hazards to the safety and efficiency of their work. It was ami-pated when the offshore operations commenced that such would be the case, and experience to date has verified this assumption. Because atmospheric conditions and wave action involve tremendous amounts of energy it is highly unlikely that it will be possible to control any but the most localized weather and wave phenomena within the foreseeable future. Thus. as long as the offshore operations involve the movement of small craft and barges over exposed waters, and the transfer of personnel and heavy equipment from these craft to either fixed structures or larger craft at close quarters, the weather and wave problem will remain. Taking into consideration the persistence of the wave and weather problem and the improbability of achieving a direct solution, the Humble Oil & Refining Company, in planning its offshore campaign investigated the possibility of forecasting wave and weather conditions in order to provide warnings of dangerous conditions and increase efficiency in day-to-day planning of work. It was recognized that predictions of wave and weather conditions based on meteorology and oceanography, both geophysical sciences, are not 100 per cent accurate and application of forecasts in the offshore work was dependent on whether they provided information which was sufficiently greater in accuracy than the layman&apos;s guess to be worth the expenditure involved. During World War 11. meteorology and oceanography were used with success in reducing danger resulting from environmental conditions and increasing efficiency of operations exposed to the elements. This success was partially the result. of improvement in the scientific techniques involved and the procurement and distribution of observational data, and partially due to the large scope of the military operations which meant that a reduction of losses of a relatively small percentage of the total cost amounted to a large figure expressed in terms of dollars. Since the offshore drilling involves an extremely large financial investment, it was considered that the experience of the Armed Services in successfully employing meteorology and oceanography might be duplicated in the oil industry. In addition. the oil industry&apos;s successful experience in utilizing seismology, geology, and terrestrial magnetism; all geophysical sciences, indicated that meteorology and oceanography, also of the family of geophysical sciences and sharing their scientific assets and liabilities, might be profitably put to use. Since the immediate problem involving the sciences of meteorology and oceanography in the offshore campaign is wave action, a program was inaugurated within the Humble Oil & Refining Company during June 1947. the purpose of which was to ascertain the applicability and limitations of wave forecasting in the offshore campaign. A summary of the effective wave forecasting techniques developed during the war was prepared in the form of a forecasting manual for the Continental Shelf off Grand Isle, Louisiana, by Bates and Glenn. After completion of this manual, experimental forecasts were prepared daily over a two-month period by Graham and Thompson to determine the accuracy of the forecasts. It was considered that the accuracy of the experimental forecasts justified a more extensive test under actual operating conditions in the offshore work and the firm of A. H. Glenn and Associates was set up under the sponsorship of the Humble Oil & Refining Company to work with the Humble Grand Isle District in providing forecasts of wave and weather conditions over a one-year period. This paper discusses the service now provided to the Grand Isle District, its applicability and limitations. TYPE OF FORECASTS REQUIRED It was apparent before the commence-mence of the forecasting service that a specialized type of forecast was required. Many of the weather elements of interest to the general public, such as rain and temperature, are of minor concern to offshore operators. On the other hand, such elements as wave height and wind speed and direction are of great concern in the offshore operations since variations in wave height of a few feet in the critical range divide safe from hazardous working conditions. To be of utility. a forecasting service for the offshore work must provide detailed forecasts of the elements which affect the operation. With this in mind, it was decided that forecasts would include the following information: average wave heights to the nearest foot, wind speeds within a range of approximately 5 miles per hour, and wind directions within 221 degrees. Since the procedure for forecasting these elements involves thorough analysis of weather data, it was decided to include a generalized forecast of weather conditions such as rain and cloud cover, although these are of secondary importance.

Jan 1, 1949

By A. H. Glenn, J. E. Graham

Oil operators engaged in drilling on the Continental Shelf of Louisiana and Texas are in agreement that adverse weather and wave action are two of the greatest hazards to the safety and efficiency of their work. It was ami-pated when the offshore operations commenced that such would be the case, and experience to date has verified this assumption. Because atmospheric conditions and wave action involve tremendous amounts of energy it is highly unlikely that it will be possible to control any but the most localized weather and wave phenomena within the foreseeable future. Thus. as long as the offshore operations involve the movement of small craft and barges over exposed waters, and the transfer of personnel and heavy equipment from these craft to either fixed structures or larger craft at close quarters, the weather and wave problem will remain. Taking into consideration the persistence of the wave and weather problem and the improbability of achieving a direct solution, the Humble Oil & Refining Company, in planning its offshore campaign investigated the possibility of forecasting wave and weather conditions in order to provide warnings of dangerous conditions and increase efficiency in day-to-day planning of work. It was recognized that predictions of wave and weather conditions based on meteorology and oceanography, both geophysical sciences, are not 100 per cent accurate and application of forecasts in the offshore work was dependent on whether they provided information which was sufficiently greater in accuracy than the layman&apos;s guess to be worth the expenditure involved. During World War 11. meteorology and oceanography were used with success in reducing danger resulting from environmental conditions and increasing efficiency of operations exposed to the elements. This success was partially the result. of improvement in the scientific techniques involved and the procurement and distribution of observational data, and partially due to the large scope of the military operations which meant that a reduction of losses of a relatively small percentage of the total cost amounted to a large figure expressed in terms of dollars. Since the offshore drilling involves an extremely large financial investment, it was considered that the experience of the Armed Services in successfully employing meteorology and oceanography might be duplicated in the oil industry. In addition. the oil industry&apos;s successful experience in utilizing seismology, geology, and terrestrial magnetism; all geophysical sciences, indicated that meteorology and oceanography, also of the family of geophysical sciences and sharing their scientific assets and liabilities, might be profitably put to use. Since the immediate problem involving the sciences of meteorology and oceanography in the offshore campaign is wave action, a program was inaugurated within the Humble Oil & Refining Company during June 1947. the purpose of which was to ascertain the applicability and limitations of wave forecasting in the offshore campaign. A summary of the effective wave forecasting techniques developed during the war was prepared in the form of a forecasting manual for the Continental Shelf off Grand Isle, Louisiana, by Bates and Glenn. After completion of this manual, experimental forecasts were prepared daily over a two-month period by Graham and Thompson to determine the accuracy of the forecasts. It was considered that the accuracy of the experimental forecasts justified a more extensive test under actual operating conditions in the offshore work and the firm of A. H. Glenn and Associates was set up under the sponsorship of the Humble Oil & Refining Company to work with the Humble Grand Isle District in providing forecasts of wave and weather conditions over a one-year period. This paper discusses the service now provided to the Grand Isle District, its applicability and limitations. TYPE OF FORECASTS REQUIRED It was apparent before the commence-mence of the forecasting service that a specialized type of forecast was required. Many of the weather elements of interest to the general public, such as rain and temperature, are of minor concern to offshore operators. On the other hand, such elements as wave height and wind speed and direction are of great concern in the offshore operations since variations in wave height of a few feet in the critical range divide safe from hazardous working conditions. To be of utility. a forecasting service for the offshore work must provide detailed forecasts of the elements which affect the operation. With this in mind, it was decided that forecasts would include the following information: average wave heights to the nearest foot, wind speeds within a range of approximately 5 miles per hour, and wind directions within 221 degrees. Since the procedure for forecasting these elements involves thorough analysis of weather data, it was decided to include a generalized forecast of weather conditions such as rain and cloud cover, although these are of secondary importance.

Jan 1, 1949

By D. H. Henley, F. F. Craig, W. W. Owens

The oil recovery performance of systems producing entirely by bottom-water encroachment has been experimentally determined in a series of scaled laboratory-model tests. The effects of well spacing, fluid mobilities, rate of production, capillary and gravity forces, well penetration and well completion techniques on the oil recovery performance have been investigated. The laboratory tests were performed using two uniform, un-consolidated sand-pack models. The models have ratios of the interwell distance to the formation thickness of 12 and 2, respectively. Tests at constant total fluid production rate were performed simulating a range of uniform reservoir characteristics and operating conditions encountered in field operations. The performance was determined by material balance and by observation of the encroachment of dyed fluids into the models. The results of the model tests agreed with those obtained mathematically when the conditions previously considered in theoretical studies were simulated, that is, when the oil and water are of equal density and no capillary forces exist. The model study of bottom-water drive indicated that certain variables can aoect the oil recovery performance to a greater degree than can be predicted by present analytical methods. In one comparison, the oil recovery at a water-oil ratio of 20 (obtained at a wide well spacing) varied as much as threefold, depending upon the system&apos;s properties and the production rate. Lesser effect of mobility ratio and no eflect of capillary forces over the range studied were observed. The test &apos;results also showed that the deeper the well penetration into the oil column, the greater the total water production to a producing WOR of 20. However, the ultimate sweep efficiency, and so the oil recovery to this level of WOR, did not vary significantly with well penetration. Horizontal fractures at the top of the formation did not significantly change the sweep characteristics of the reservoir models when values of radius and fracture capacity encountered in actual reservoirs were used. Impermeable pancakes at the bottom of the well moderately increased the oil recovery efficiency both at water breakthrough and at high water-oil ratios. A method is outlined by which the oil recovery performance of other uniform bottom-water drive systems can be estimated from the information obtained in these model tests. INTRODUCTION When oil is produced from a well which partially penetrates an oil zone completely underlain by water, the water rises directly beneath the well in a symmetrical cone when the system is uniform. Two different flow mechanisms can cause the water cone to form—coning and bottom-water drive. In coning, the aquifer is relatively inactive and the cone is formed beneath the well by the pressure gradients associated with the oil flow to the well. The oil can be produced by a solution-gas drive, an edge-water drive or other driving forces in the interwell area. In a bottom-water drive, the driving force for oil production comes from an upward encroachment of the underlying active aquifer. Two papers have analyzed the theoretical performance characteristics of bottom-water drive reservoirs. In the initial mathematical investigation, Muskat&apos; established the equations which determine the pressure distribution in this type of reservoir and solved these equations for certain conditions. Specifically, it was assumed that the water and oil had equal mobilities and equal densities, there were no capillary forces, the pressure throughout the oil zone remained above the bubble-point pressure, a constant pressure existed at the initial water-oil contact and the oil was completely displaced by the encroaching water. These assumptions were used in obtaining analytical solutions. In general, Muskat found that the sweep efficiency to initial water breakthrough to the well was larger for the thicker oil zones, the closer well spacings, the lower ratios of vertical to horizontal permeabilities, the smaller the penetration of the well into the oil zone and the smaller the bore size of the well. The production history after water breakthrough was expressed as a volumetric sweep efficiency at a given producing water-oil ratio. The results indicated that cumulative oil production at producing water-oil ratios of 10 is less affected by the well spacing than is the water-free production history. Muskat studied well spacing which today would be regarded as close. The maximum value of his dimensionless well spacing (ratio of interwell distance to formation thickness) was 4.3. This would require the development of a 50-ft-thick oil sand on less than 10-acre spacing if the vertical and horizontal permeabilities were equal, with

By R. F. Nielsen, D. E. Menzie

The object of this study was to determine if crude oil could be produced successfully by a process of crude oil vaporization using carbon dioxide repressuring. This process appears to have application to highly fractured formations where the major oil content of the reservoir is contained in the non-fractured porosity with little associated permeability. Crude oil was introduced into the windowed cell and carbon dioxide was charged to the cell at the desired pressure. A vapor space was formed above the oil, and the crude oil-carbon dioxide mixture was allowed to come to equilibrium. The vapor phase was removed and the vaporized oil collected as condensate. Samples of all produced and unproduced fluids were analyzed. Tests were also performed to evaluate the amount of vaporized oil that can he produced by rocking from a high to a lower pressure. The carbon dioxide repressuring process was applied to a sand-filled cell to investigate the performance in a porous medium. A test was performed to evaluate how the condensate recovery changes as the size of the gas cap in contact with the oil changes. INTRODUCTION This study has been directed toward a relatively new process of vaporization of crude oil designed to increase ultimate production of hydrocarbons through the application of carbon dioxide to an oil reservoir. Suggested advantages of carbon dioxide repressuring of a petroleum reservoir are: (1) reduction in viscosity of liquid hydrocarbons due to the solubility of carbon dioxide in crude oil, (2) swelling of the reservoir oil into a larger liquid-oil volume with a resulting increase in production and decrease in residual oil saturation due to an increase in the relative permeability to oil, (3) displacement of more stock-tank oil from the reservoir since the residual liquid is a swelled crude oil, and (4) gasification of some of the hydrocarbons into a carbon dioxide-hydrocarbon vapor mixture. Balanced against these advantages are several detrimental factors which must be evaluated; i.e., high compression costs and corrosion of well equipment and flow lines. Some of the more outstanding contributions to the study of carbon dioxide injection have been reviewed in order to furnish a basis for a continuation of research pertaining to this method. The literature reviewed1-8 has been limited to that dealing with carbon dioxide repressuring processes or with carbon dioxide-crude oil-natural gas phase behavior. Articles relating to carbonated water injection and literature published on the use of low pressure carbon dioxide gas injection in water flooding have not been included in this study. In 1941 Pirson5 suggested the high pressure injection of carbon dioxide into a partially depleted reservoir for the purpose of causing the reservoir oil to vaporize and thus produce the oil as a vapor along with the carbon dioxide gas. By reducing the pressure on this produced mixture of hydrocarbons and carbon dioxide at the surface, it was proposed to separate the hydrocarbons from the carrier gas. He theorized that essentially all the oil in a reservoir could be produced by simply injecting enough carbon dioxide to vaporize the residual oil. This present investigation deals with the vaporization of a crude oil by carbon dioxide, the molecular weight and gravity of the vaporized oil product and the characteristics of the residual oil after several repressuring cycles with carbon dioxide. An attempt is made to evaluate the merits of a vaporization process for the crude oil rather than a flow process where the oil recovery is determined by relative permeability considerations. Such a vaporization of crude oil by carbon dioxide repressuring appears to have possible use in a highly fractured formation where the major oil content of the reservoir is contained in the non-fractured porosity with little permeability. The carbon dioxide flows into the fractures, contacts the crude oil in the matrix and vaporizes part of the crude oil; this vaporized oil is produced and recovered and the carbon dioxide is reinjected again. The specific problem of this study is to attempt to answer this question; Can crude oil be produced successfully (technically, but without economic considerations) from a petroleum reservoir by a process of vaporization of the crude oil by carbon dioxide repressuring? DEFINITION OF TERMS AS APPLIED IN THIS STUDY Carbon Dioxide Contact: One cycle in which carbon dioxide was injected and bled off. Condensate: The hydrocarbon liquid which was condensed out of the mixture of hydrocarbon-carbon dioxide vapor upon reduction of the pressure of the vapor. Hydrocarbons Produced (HCP): All the hydrocarbon!, which were vaporized by the carbon dioxide repressuring process and were removed from the cell during any specific cycle or carbon dioxide contact. Hydrocarbons Unproduced (HCU): All the hydrocarbons which were not vaporized by the carbon dioxide

By N. J. Grant, C. C. Wang

The Ti-Cr-O ternary system has been studied in detail near the titanium-rich corner within the limits of 10 wt pct 0, and 20 wt pct Cr. Studies were extended, but not in detail, to the region beyond 25 wt pct 0, (50 atomic pct) and 62 wt pct Cr (60 atomic pct). Four isothermal sections at 1400°, 1200°, 1000°, and 800°C are presented as well as two vertical sections at 1 and 2 wt pct 02. DURING the last decade much interest has been shown in the development of high strength titanium alloys for high temperature and corrosion resistant applications. Extensive research is being carried out at present, as the current literature indicates, in order to study the properties of titanium and to develop improved alloys. Two of the important alloying elements in commercial titanium alloys are chromium and oxygen and it would be desirable to know their combined influence upon titanium. For this purpose the present work was carried out to investigate the titanium-rich corner of the ternary system TiICr-0. The binary systems Ti-Cr and Ti-0 have been published recently. The Ti-Cr system was studied by several investigators " and their results are in close agreement. The eutectoid decomposition of the B phase has been shown to be extremely sluggish. TiCr, was the only intermetallic compound found in this binary system and was formed at 1350°C by a transformation from the p phase. TiCr? was established as the cubic C 15 (MgCu,) type of structure with 24 atoms per unit cell and was designated as the y phase. This terminology will be adopted in the present work. There was disagreement about the actual composition of this compound among the several investigators, although it is evident from their data that the compound probably has a solubility range of about 2 to 3 pct and is in the vicinity of 65 pct Cr. It has been indicated recently that a high temperature modification of this y phase (TiCr,) existed at a temperature above 1300°C." &apos; This high temperature modification was identified as a hexagonal C 14 (MgZn,) type of structure with 12 atoms per unit cell. The exact transformation temperature from the high temperature phase to the low temperature phase has not been established. A considerable hysteresis was observed and, due to the sluggishness of this transformation, the high temperature phase often co-existed with the low temperature phase at temperatures below 1300°C. A preliminary study of several Ti-0 compounds and the Ti-0 system had been carried out by Ehr-1ich."-"&apos; The most complete binary Ti-0 system was the one reported recently by Bumps, Kessler, and Hansen." The first intermediate phase found in the system was the 8 phase which formed by a peritec-toid reaction of the phases a and Ti0 at temperatures below 925 °C. This reaction is extremely sluggish. The structure of this 8 phase was tentatively identified by these authors as being tetragonal and the lattice constants were found as c,, - 6.645A, a,, = 5.333A and c/a = 1.246A. Experimental Procedure The raw materials used for this investigation were TiO,, electrolytic chromium, iodide titanium, and sponge titanium. The TiO, was in the form of powder of chemically pure grade (99.8 pct pure). The chemical analysis of the electrolytic chromium was: 0, 0.50 pct; Fe, 0.07; Cu, N, and C, 0.01; and Pb, 0.001. The oxygen in the chromium was calculated as part of the final oxygen content of the alloys. The alloys were prepared by the cold crucible method using a tungsten arc. The entire system was evacuated and flushed with purified helium three times and then filled with helium. Each alloy was melted, turned over, and remelted at least four times to insure homogeneity. The total melting time was generally from 6 to 10 min. A master alloy of 25 pct 0,-75 pct Ti was prepared to facilitate alloying by melting compacts of TiOl powder with either iodide or sponge titanium, yielding the compound TiO. It was found necessary to bake the TiO, powder compact at about 150°C to remove adsorbed moisture. This was done to prevent the disintegration and spattering of the compact when the arc was struck. TiO, powder dissolved quite readily into the melt and no other trouble was encountered.

Jan 1, 1955

By A. U. Seybolt

In part 111&apos; of this series it was shown that during the selective oxidation of a 3 1/4 pct Si-Fe alloy in damp hydrogen, only silica, (observed at room temperature) as low cristobalite or low tridy-mite or both, was formed as an oxidation product. In some in- „ stances where the film was fairly thin (probably well under 100A) there was some suggestion of an amorphous form of SiO2. The present investigation of oxidation rate showed that the selective oxidation of silicon-iron can be rather complicated, and apparently impossible to rationalize in an unequivocal manner. In some temperature regions, notably near 800" and 1000°C, the data seem to obey the familiar parabolic rate law. However, at intermediate temperatures complications were noted, some of which are possibly due to the order-disorder reaction in the silicon-iron solid solution. IN an earlier report&apos; it was shown that during the oxidation of 3 1/4 pct Si-Fe alloys in H2O-H2 atmospheres only silica films were formed in the temperature range from 400° to 1000°C in hydrogen nearly saturated with water at room temperatures, or at dew points as low as -45°C. In the work to be reported here, some observations are made on the rate of oxide film formation. As in the earlier investigation, electron diffraction patterns generally showed either low tridymite or low cristobalite or both, except for some very thin films. These sometimes showed diffuse rings, presumably due to a very small crystallite size, or in a few cases, diffuse bands probably caused by an amorphous film. EXPERIMENTAL PROCEDURE Vacuum-melted silicon iron made of high-purity materials was rolled into strips 0.014 in. thick, and cut into samples 1/2 in. wide by 1 in. long. Chemical analysis showed 3.2 pct Si and 0.002 pct C. All samples were surface abraded with 600-grit paper, were solvent cleaned, and then placed in an paper,apparatus containing a "Gulbransen type"2 micro-balance. Here the gain in weight of the samples of about 5 sq cm area could be followed as a function of time during the oxidation caused by the water in atmospheres of various controlled water-hydrogen ratios. The water-hydrogen ratios can most easily be described as varying from a dew point of 0°C (PH2O-p^2 = 6.2 x 10-3 , to K (P j -40°C (PH2O/PH^= 1.3 X 10-* Most of the experiments were conducted at the 0°C dew-point atmosphere because drier atmospheres caused so little gain in weight that the accuracy of measurement was poor. Because of this, only the data obtained at PH2O,/P,,,= 6.2 x X3 will be reported. The temperature range extended from 800" to 1000°C; and most of the oxidation runs lasted for about 24 hr. The reproducibility of any reading was about ± 1 ?, but the sensitivity of the balance was about 0.2 ?. The atmosphere, flowing at 200 cm per-min, was preheated to the furnace temperature before contacting the specimen. While the gas flow caused a measurable lift on the sample, it was ordinarily sufficiently constant so that it was not an appreciable source of error. X-ray and electron diffraction checks of the samples before and after oxidation showed no evidence of preferred orientation, either on the metal samples or on the silica films formed. EXPERIMENTAL RESULTS The data obtained are summarized in Table I, and some are given in detail in Figs. 1 to 4. In the fourth column of Table I, kp refers to the parabolic rate constant in the expression (?/cm2)2 = kpt + c [1] where ? = micrograms gain in weight kp = parabolic rate constant in units r2 /cm4 t = time in minutes c = constant It will be noted that in many cases no value for kp is given; this is because in these instances the data did not obey the parabolic rate law. The silica film thicknesses given in the last columns are values calculated from the weight gain, an average tridy-mite-crystobalite density, and by assuming a perfectly plane surface. Fig. 1 shows the data plotted in the form of Eq. [I], hence a linear plot indicates parabolic behavior. It has been frequently observed in the literature that

Jan 1, 1960

By A. Ghosh, T. B. King

The kinetics of the discharge reaction: 20&apos;- (in silicate melt) = O,(g) + 4e- at a platinum anode in lithium silicate melts have been studied al 1350°C by galvanostatic methods. Plots of the sleady-state overpotential, q, as a function of the logarithm of the current density, i, showed injlections and were linear only at high current densities. The value of the overpotential was influenced by bubbling gas through the electrolyte. The ocer potential was also studied as a function of time. The rise and decay of overpotential were very slow processes. At low current densities transport is the likely rate-controlling process but at high current densities passivation of the electrode, Presumably by an oxide film on the surface, seems to be a contributory functor. IT is well-established that molten silicates behave as electrolytes&apos;5 and, except in a few cases,6 conduction is entirely ionic. Moreover, it is supposed that a possible, and perhaps predominant, mechanism for phase boundary reactions between metals and slags is similar to that in corrosion whereby anodic and cathodic processes occur at unrelated sites, the metal serving to conduct electrons.1&apos;8 Thus electrochemical studies of some slag-metal reactions would seem to be a useful way to diagnose the rate-controlling steps in the overall reaction. The electrochemical method is, in principle, a better diagnostic tool than the direct chemical method for the following reasons: 1) The partial electrochemical reactions, which are simpler than the overall reaction, may be studied individually. 2) The rate of reaction can be controlled at will and independently of the concentrations of reactants. 3) Fast reactions can be studied by relaxation methods.&apos; Esin and his coworkers5&apos;10"12 have pioneered such studies in silicates and have deviloped some ingenious techniques. Not all of their findings, however. can be accepted without a good deal of further work. In this investigation, the kinetics of the oxygen discharge reaction: 202- (in silicate melt) = Oz(g) + 4e- [I] at a platinum electrode were studied by both steady-state and transient galvanostatic techniques. Interest in this reaction was first developed as a result of the findings of Fulton and chipman13 that the reduction of silica, in a silicate slag, by carbon, dissolved in liquid iron, is a very slow reaction. Subsequent work, for example, by Rawling and ~lliott,&apos;~ has demonstrated that the reaction under these conditions must be slow, because the rate is limited by diffusion of oxygen in the iron to the metal-crucible phase boundary at which a CO bubble may be nucleated. Further work by Tarassof,&apos;~ in which the reduction of silica by aluminum dissolved in copper was studied, has shown that under these conditions, where carbon monoxide evolution is not involved, control of the reaction rate resides in diffusion of silica in the slag phase. However, there is no practical way of inducing sufficient convection in the system to make it clear that the phase boundary reaction is indeed fast. The overall reaction of silica reduction involves the discharge of silicon ions at cathodic sites and oxygen ions at anodic sites. In the examples cited, the discharged ions are dissolved in a liquid metal. In the present study of oxygen ion discharge, gaseous oxygen may be evolved at high current densities or oxygen may simply dissolve, possibly as oxygen molecules, in the silicate at very low current densities. The discharge of an oxygen ion at an anode must, in silicates less basic than the orthosilicate composition, be preceded by a reaction in the vicinity of the electrode, such as: which makes oxygen ions available. Platinum was chosen as the working electrode since it is comparatively inert to oxygen and is, therefore, expected to come rapidly into equilibrium with the electrolyte and with gaseous oxygen. Minenko, Petrov, and Ivanova16 have measured the electromotive force at a platinum electrode in molten silicates as a function of the partial pressure of oxygen in the atmosphere, the concentration of oxide ions in the melt, and the temperature. They found platinum to behave as a reversible oxygen electrode. At two different oxygen pressures, Po2 (I) and Pq (11). the electromotive force is given by: where F is the Faraday constant, equal to 23,060 cal per v equivalent, indicating that the electrode reaction is as written in Eq. [I.]. Platinum has been similarly used in molten silicates by other inve~ti~ators. "&apos;~~ In this investigation platinum was used only as an anode, since a current deposits other elements on its surface and changes its characteristics.

Jan 1, 1970