Search Documents

By Everett G. Trostel

AMERICAN industry in 1943 emerged from the construction phase into the production phase, and American military operations passed from preparation into full action in the many theaters of the global war. The increased pace of industrial and military operations has resulted in a tremendous demand for petroleum and its products.

Jan 1, 1944

By Hoyt Gale

RECENT work on borate deposits near Kramer, in the extreme southeast corner of Kern County, California, is of special interest to those who are making a study of the mode of origin of the borate minerals colemanite and ulexite. A valuable clue to the mode of origin of colemanite in its present known deposits is given in a paper by W. F. Foshag1, of the United States National Museum. Colemanite is found in or near original deposits of ulexite, from which it is supposed to have been derived by a change in the rate of movement or the character of the ground water. Indications that an alteration of this sort had produced colemanite were first recognized by the writer' in specimens collected in the Kramer district in 1920, and sent to W. T. Schaller, at U. S. Geological Survey, for identification. The identity of the two borate minerals in these specimens was not at once determined, but the relations of the minerals as seen in the specimens afforded a manifest clue to the origin of the deposits. Similar specimens were obtained by the writer from deposits in death Valley soon after he had examined the deposits near Kramer. After studying the specimens submitted to him Dr. Schaller wrote as follows: "I have finally positively identified the boron minerals you sent me with your letter of Sept. 27. The `white fibrous mineral like ulexite' is ulexite; the harder nodules' in the clay are colemanite, apparently formed from the ulexite as a result of leaching, with recrystallization in place-a theory that Foshag is working on." The present paper is a report on the facts observed at. the deposits near Kramer, and some general observations on the geological relations noted, which, unfortunately, still form only a very incomplete record.

Jan 2, 1926

By J. C. Scully, G. Sanderson

The electrolytic formation of y hydride in thin foils of Ti-5Al-Z.5Sn alloy and four Ti-A1 binary alloys has been studied by electron microscopy and electron diffraction. Two orientation relationships have been found: THE adsorption of hydrogen by titanium alloys from aqueous solutions has been widely reported. This can occur, for example, in both alkaline' and acidic2 pickling baths, in chemical polishing374 and electro-polishing Solutions,3,4 during cathodic polarization5" and under certain corrosion conditions,7,8 Etching reagents may also produce visible precipitates, sometimes after an aging period.9 During an investigation into the stress corrosion susceptibility of a titanium alloys by thin foil electron microscopy many observations have been made of hydride precipitation which has been deliberately promoted by techniques that are described below. The characteristics of hydride precipitation are reported and the observed crystallographic orientation relationships are discussed with reference to distortion in the titanium lattice created by the presence of the hydride. EXPERIMENTAL TECHNIQUE One grade of commercial titanium and five alloys were examined. Their composition and hardness values are shown in Table I. All the materials were in the form of thin sheet, 0.05 to 0.065 cm thick, which had been annealed after cold rolling. Foils suitable for transmission electron microscopy were made in two ways: a) by chemical polishing; and b) by elec-tropolishing. The solution used for chemical polishing was a mixture of 44 pct HF and 73 pct HNO3 in the volumetric ratio 2:3. During this polishing specimens were manually moved up and down in the solution. The reaction was veFy rapid, specimens thinning to foil thickness (2000A) in 5 min. Since chemical polishing solutions tend not to cause hydride contamination if they are kept cool3 no attempt was made to prevent the solution from becoming hot during the thinning operation. Electropolishing was performed at -30° C with a mixture3 composed of 295 cu cm methyl alcohol, 175 cu cm n-butyl alcohol, and 30 cu cm perchloric acid with an applied voltage of 40 v after chemically thinning specimens to approximately 0.017 cm thickness in a cool solution of 44 pct HF, 40 vol H2O2, and water in the volumetric ratio 1:6:3. EXPERIMENTAL RESULTS 1) Ti-5A1-2.5Sn Alloy. The Ti-5A1-2.5Sn alloy was severely contaminated by hydrogen during the chemical polishing. Foils obtained in this way contained large amounts of the y hydride phase. A typical micrograph is shown in Fig. l. The laths were identified as the hydride phase by selected-area diffraction of a large number of foils examined in a tilting stage that could be turned through 40 deg. Using the lattice spac-ings of the alloy obtained by X-ray diffraction as a standard the a value of the hydride was determined fromo the electron diffraction patterns to be 4.38 to 4.40A. The accuracy of this figure is only about ±2 pct. Further evidence of the identification was obtained by vacuum annealing chemically polished foils of the alloy at 500°C. This resulted in the dissociation of the hydride with the production of dislocations and possibly vacancy loops as shown in Fig. 2. The hydride

Jan 1, 1968

By Arthur Notman

THE mineral industries in this country have now had about a year of national planning. Al. though the period is short, the volume of activity and legislation designed to make that planning effective has been nothing short of enormous. Those who have been privileged to see and study a few of the codes to regulate our mineral industry, such as those for oil, coal, steel, and copper, are driven to the conclusion that nothing was really known about the proper way to conduct those industries in this country prior to June, 1933; or if anything was known, nobody in actual practice made use of that knowledge. And yet those industries, in days gone by, helped to make this country the most prosperous in the world, and to maintain a standard of living even today higher than that of any other country. Without wishing to assume any first-hand knowledge of the Russian standard of living, I must confess that the evidence seems to indicate that even with dictatorial authority, national planning encounters unexpected difficulties. Perhaps what really wants

Jan 1, 1935

By Nelson P. Hulst

To those who have had the happy privilege of friendship with George W. Goetz, the announcement of his death has brought great sadness. He was born in Milwaukee, Wisconsin, February 17, 1855, and died January 15, 1897. In his boyhood days, when I first came to know him, his frank, trustful manner; his eyes brimming with truthfulness; his eagerness, never obtrusive, to gain knowledge from all whom he met; and his equal readiness to give without ostentation of his store, constituted a personality which at once commanded confidence and won friendship. I am told that as a scholar of five years he was conspicuous for brightness, a show-pupil, who was called on to recite when visitors were present at school. Yet this in no way spoiled him. His modesty was too strong a trait in his character to be overcome by any attention which might, be expected to arouse vanity. In his simple-heartedness he was pleased then, as he always was in his maturer years, to give of his knowledge for the gratification of his listeners, with never a thought of himself. So strong was this characteristic that in a brief autobiography, in the form of a letter to his wife and children, found among his papers, he excuses himself to them for recounting what he had accomplished in his life-work. As a preface to this autobiography (which, it seems, was prepared on the eve of a sudden journey to California, taken February, 1895, for his health) he says: " I am writing this rather hastily, and I

Jan 1, 1898

By R. Q. Shotts

Data are presented which show that fractions of varying densities from the same coals are oxidized at different rates by nitric acid. From oxidation data, the approximate quantity of "bright" and "dull" components may be calculated. Definite relationships between oxidation rate and rank are shown for density fractions from at least two bituminous coals. IN 1945, the Alabama State Mine Experiment Station initiated a program on the determination of fusain in certain coals of the state.1 Because of the lack of equipment and personnel necessary for microscopic examination, the chemical method2 was used exclusively. During studies of the distribution of fusain in fractions of various sizes and densities on a medium volatile coal, the author noted a higher rate of oxidation of the nonfusain part of the coal in the lower density fractions and the difference in rate became more marked the shorter the oxidation period used. Since durain and other "dull" components of coal have been reported3,4,5 to have higher densities than vitrain and the bright components, it appeared probable that the observed differences in rates of oxidation in the different density fractions were due to variations in petro-graphic composition. Such effects have been noticed by other workers.2,3 In order to obtain further evidence on this point, several Alabama coals of different rank have been separated into three or more fractions on the basis of density and their rates of oxidation determined, using the procedure specified for the determination of fusain, except that measurements were made at short time intervals as well as for the longer periods specified in the regular procedure. Significant differences in the rates of oxidation of the nonfusain part of the various fractions have been observed, and it is believed that studies of this type may make possible the identification of individual petrographic components or lead to methods for their semiquan-titative estimation. Properties of the Coals: Analyses and some properties of the whole coals studied are given in table I. The range in rank of the coals is not the widest possible within the state, but samples of the low volatile coals that occur in thin beds in the northeastern part of the state, were unavailable. The Clements bed is not, at present, considered workable. The coal is of medium volatile rank, quite friable, and very strongly swelling. Analyses of different size fractions show that the larger sizes are of higher rank than the smaller ones. Material passing the No. 50 sieve (all sieve sizes refer to the U. S. Standard Series) is close to high volatile A in rank, except for the size passing a No. 200 sieve, in which fusain is partially concentrated. Because of the variation in rank of the sizes of Clements coal, oxidation studies were made of two widely different size ranges. The + 1-in. material was crushed on rolls to about 1/8 in. and separated into five fractions by float-and-sink treatment in a benzene-carbon tetrachloride mixture. The — No. 4 + No. 8 and the — No. 4 + No. 50 size ranges tested overlap but the latter size was studied last with the expectation that it would include more oxidizable material than the first size. This proved not to be the case. Yields and properties of the specific gravity fractions oxidized are shown in table II. Milldale bed coal probably represents, as nearly as it is possible to do so, the "average" coal of the state. The material passing a No. 4 sieve was the only size range oxidized. It was divided into four specific gravity fractions. As in every case the heaviest fraction, which was essentially rock, was discarded. The Black Creek is the most extensive in area of

Jan 1, 1951

By R. Q. Shotts

Data are presented which show that fractions of varying densities from the same coals are oxidized at different rates by nitric acid. From oxidation data, the approximate quantity of "bright" and "dull" components may be calculated. Definite relationships between oxidation rate and rank are shown for density fractions from at least two bituminous coals. IN 1945, the Alabama State Mine Experiment Station initiated a program on the determination of fusain in certain coals of the state.1 Because of the lack of equipment and personnel necessary for microscopic examination, the chemical method2 was used exclusively. During studies of the distribution of fusain in fractions of various sizes and densities on a medium volatile coal, the author noted a higher rate of oxidation of the nonfusain part of the coal in the lower density fractions and the difference in rate became more marked the shorter the oxidation period used. Since durain and other "dull" components of coal have been reported3,4,5 to have higher densities than vitrain and the bright components, it appeared probable that the observed differences in rates of oxidation in the different density fractions were due to variations in petro-graphic composition. Such effects have been noticed by other workers.2,3 In order to obtain further evidence on this point, several Alabama coals of different rank have been separated into three or more fractions on the basis of density and their rates of oxidation determined, using the procedure specified for the determination of fusain, except that measurements were made at short time intervals as well as for the longer periods specified in the regular procedure. Significant differences in the rates of oxidation of the nonfusain part of the various fractions have been observed, and it is believed that studies of this type may make possible the identification of individual petrographic components or lead to methods for their semiquan-titative estimation. Properties of the Coals: Analyses and some properties of the whole coals studied are given in table I. The range in rank of the coals is not the widest possible within the state, but samples of the low volatile coals that occur in thin beds in the northeastern part of the state, were unavailable. The Clements bed is not, at present, considered workable. The coal is of medium volatile rank, quite friable, and very strongly swelling. Analyses of different size fractions show that the larger sizes are of higher rank than the smaller ones. Material passing the No. 50 sieve (all sieve sizes refer to the U. S. Standard Series) is close to high volatile A in rank, except for the size passing a No. 200 sieve, in which fusain is partially concentrated. Because of the variation in rank of the sizes of Clements coal, oxidation studies were made of two widely different size ranges. The + 1-in. material was crushed on rolls to about 1/8 in. and separated into five fractions by float-and-sink treatment in a benzene-carbon tetrachloride mixture. The — No. 4 + No. 8 and the — No. 4 + No. 50 size ranges tested overlap but the latter size was studied last with the expectation that it would include more oxidizable material than the first size. This proved not to be the case. Yields and properties of the specific gravity fractions oxidized are shown in table II. Milldale bed coal probably represents, as nearly as it is possible to do so, the "average" coal of the state. The material passing a No. 4 sieve was the only size range oxidized. It was divided into four specific gravity fractions. As in every case the heaviest fraction, which was essentially rock, was discarded. The Black Creek is the most extensive in area of

Jan 1, 1951

By W. L. Zeigler

DURING the middle 1880s, shortly after the discovery of silver-lead ores in the Coeur d'Alene district of northern Idaho, it became apparent that concentration of the ores would be necessary to obtain a profitable product. Too much siliceous material was present for direct smelting, and the majority of the ores found at depth were too low in metallic content for economic smelting processes at the time. As the ores occurred in quartzite shear zones with siderite and quartz gangue, a large quantity of waste material was present in all the mines. As the galena was not finely disseminated, this made possible relatively good extraction of the argentiferous galena by coarse concentration. The first concentrators consisted mainly of coarse crushing, screening and jigging, principally by Harz jigs, the slimes being treated on buddies. Later Wilfley tables took the place of sand jigs and vanners superseded the buddies. Because of the marketing conditions, no attempt was made until 1900 to effect a recovery on the zinc minerals present, which were found associated in varying amounts with the galena. All through this period, the greater part of the production was obtained from mines containing ore assaying high in lead and low in zinc. Parts of some ore bodies would be reversed in this respect, so that ores high in zinc were left intact. During the decade after 1910, several important mines, The Success and The Interstate Callahan, containing ores high in zinc, were put into operation and were a material aid in the needed zinc production during World War I. Gravity concentration by jigs and tables was used during this period, with bulk flotation increasing in popularity for the treatment of the fine material that had already been treated by ordinary slime concentrating machinery. No extra fine grinding for flotation concentration was thought profitable at the time. TAILINGS DISCHARGED INTO STREAMS From the start of mining and milling operations in this district until 1904, no attempt was made by the various mills in the upper district to impound or stack their tailings. They discharged them directly into the adjacent creeks or streams, to be carried away by high water. The Bunker Hill and Sullivan and the Last Chance mines, both in the relatively flat valley of the district, stacked huge piles of the coarse jig tailings on the near-by river bottom. Rain and snowfall are heavy in the Coeur d'Alene district, as it is on the heavily timbered Pacific slope of the Bitter Root Mountains. A heavy runoff occurs every spring and there is an occasional flood of disastrous proportions when warm "Chinook" winds accompanied by rain

Jan 1, 1947

By D. J. McAdam

Results of investigation of corrosion-fatigue of metals at the U. S. Naval Engineering Experiment Station, Annapolis, Md., have been discussed by the writer in several recent paper~.1,2,3,4 In those papers references were also given to the work of Haigh in 1917.= Efforts by the writer to obtain a better understanding of some of the factors involved in corrosion-fatigue finally developed into a general investigation of the effect of time and cyclic stress on corrosion of metals. Corrosion-fatigue of Metals As described in the papers mentioned, rotating-cantilever specimens, conically tapered so that the stress is nearly uniform over a length of about 1.5 in., were subjected to simultaneous fatigue and corrosion. For this purpose a stream of water was diagonally applied so as to sweep the specimen from the outer to the inner fillet and surround the stressed surface with water. The fresh water is a calcium carbonate water, the composition of which has been given in a previous paper.2 The salt water is Severn River water having a saline content about one-third that of sea water. The previous papers described results obtained with ferrous and non-ferrous metals. The experiments showed that even slight corrosion simultaneous with fatigue may cause failure at nominal stresses far

By D. J. McAdam

RESULTS of investigation of corrosion-fatigue of metals at the U. S. Naval Engineering Experiment Station, Annapolis, Md., have been discussed by the writer in several recent papers. 1.2.3.1 In those papers references were also given to the work of Haigh in 1917.6 Efforts by the writer to obtain a better understanding of some of the factors involved in corrosion-fatigue finally developed into a general investigation of the effect of time and cyclic stress on corrosion of metals. Corrosion fatigue of Metals As described in the papers mentioned, rotating-cantilever specimens, conically tapered so that the stress is nearly uniform over a length of about 1.5 in., were subjected to simultaneous fatigue and corrosion. For this purpose a stream of water was diagonally applied so as to sweep the specimen from the outer to the inner fillet and surround the stressed surface with water. The fresh water is a calcium carbonate water, the composition of which has been given in a previous paper .2 The salt water is Severn River water having a saline content about one-third that of sea water. The previous papers described results obtained with ferrous and nonferrous metals. The experiments showed that even slight corrosion simultaneous with fatigue may cause failure at nominal stresses far

Jan 1, 1928

By W. G. Jewitt

YELLOWKNIFE, the most northerly Canadian gold mining district, is once more in the throes of a boom. Touched off by spectacular and well-publicized diamond-drilling results on the property of Giant Yellowknife Gold Mines, Ltd., mining companies and the general public are competing for mining claims and for the shares of companies owning mining claims in the area, with little regard for values. Such a stock-market boom has various unfortunate consequences but undoubtedly one beneficial result is that considerable amounts of money are made available for serious development. The Yellowknife mining area lies on the north shore of Great Slave Lake, in the Northwest Territories, at a latitude of approximately 62°30' north. The topography is a low-relief phase of that usual in the Canadian Laurentian shield. Roughly, one third of the surface is lake-covered, one third muskeg or overburden, and one third is bare

Jan 1, 1944

By P. Shahinian, J. Weertman

Minimum creep rates of nickel samples were measured in the stress region of 2.5x107 to 2.8xl0 dyne per sq cm and the temperature region of 400° to 1100°C. The creep rate seems to be proportional to (stress) at stresses below 7x10H dyne per sq cm. The activation energy of creep is approximately 65,000 cal per mol. IN a recent theory' of steady-state creep which is based on Mott's dislocation climb mechanism, the following creep equation was derived for creep in polycrystalline metals (if where K is creep rate, Q the activation energy of self-diffusion, S the entropy of activation of self-diffusion, L' the grain size, L the subgrain size, b the length of the Burgers' vector of a dislocation, u the shear modulus, u the stress, a the critical shear stress, M the density of active Frank-Read sources, v the vibrational frequency of a vacancy, and kT has its usual meaning. This equation predicts a creep rate which depends on the stress through a power law at low stresses. At high stresses the creep rate increases much more rapidly with stress. The theory breaks down for stresses great enough that the inequality holds true. It was the purpose of the present in-

Jan 1, 1957

By Richard P. E. Hermsdorf

IN the nonferrous sessions this year, magnesium wiggled its way into a dace of prominence such as it has never before enjoyed. This was evidenced not only by the number of papers presented on that metal but by the attendance at the meetings. The atmosphere permeating these magnesium meetings was similar to that which exists in a family with a new baby. Everybody crowded around to see what it looked like and then wondered whether it would be a success and credit to the family. Well. magnesium appeared to be a vigorous youngster, full of life, and raring to go. A close relative of maenesium named " aluminum, although much more grown up, also attracted much attention. From the activity and spirit in these sessions

Jan 1, 1944

By T. R. Wright

IN few mining regions in the world are the ores so varied and complex as in the Andes of central Peru. Consequently, in few localities is one company engaged in so many and such diverse metallurgical operations as the Cerro de Pasco Copper Corp. Concurrent with the mining of complex lead-zinc ores in Peru, and the consequent expansion of the Corporation's metallurgical activities, a department of metallurgical research was established in 1927 at La Orova. Facilities were provided for research in ore dressing, hydronivtallurgy pyrometallurgy, electrometallurgy, and analytical chemistry. In addition to laboratories. various pilot plants were built, including a concentrator, leaching plant, "by-product" smelter, and electrolytic refineries. These pilot plants are not diminutive units; they are designed and equipped as semicommercial plants for operation on a continuous 24-hour basis thus assuring the duplication of pilot plant results in actual practice. In general, the sequence in the development of metallurgical operations hasbeen as follows: (1) investigations in the laboratory to determine the most effective and economical method of treatment; (2) continuation of the research project on a pilot-plant scale when the evaluation of the laboratory

Jan 1, 1945

By Edward Steidle

TWO years ago the Committee on Latin American Education Relations, Mineral Industries Education Division, started a study of mineral industries education in the Latin Americas. Information was obtainable only with great difficulty. Some information was available piecemeal but no complete resume had ever been assembled. Initial assistance was gained from the United States Office of Education and the Pan American Union. This, and first-hand knowledge of the writer, provided a list of colleges and universities which were believed to offer work lead. ing to a degree in one or more branches of the mineral industries. Detailed information could be obtained only by direct contact with each university through air mail service. Questionnaire letters were sent to officials of 34 colleges and universities. Twenty-one gracious replies were received. Fourteen of the colleges and universities concerned offer curricula in mining, five in metallurgy, three in petroleum, seven in geology, one in geographical engineering, one in topographical engineering, and one in geophysics. Two institutions offer advanced training in petroleum engineering. No institution offers any courses under the caption of ceramics or fuel technology.

Jan 1, 1945

By Nathan C. Rockwood

BASIC mineral commodities may be divided into two general classifications in their market or price characteristics. In one class are commodities sold on a world-wide basis, as gold, silver, nickel, asbestos and petroleum, and in the second are those produced and sold locally. Of course, no precise line of demarcation exists between the two; coal, for instance, belongs more or less in both. If there are enough producers of any commodity to prevent control of production by any one person or group, a free market then exists and the price in a buyer's market is determined by the most favored producer-meaning the producer, with the lowest production cost or the lowest cost of transportation, or both, to the particular market, or place of use. With minerals in the first classification, their high intrinsic value far outweighs the transportation cost and a uniform market price is accepted as an essential element in the economy of distribution. But with common minerals of small. intrinsic value and relatively high transportation costs, economists are reluctant to admit that a uniform price may also be an essential element in distribution.

Jan 1, 1940

By Paul F. Kerr

QUARTZ of a certain kind, is one of our strategic minerals, and Brazil is probably the one important available source. Crystals of quartz of suitable size and perfection for piezoelectrical application are rare; their most outstanding use is in radio work. Clear quartz, or "crystal," free from twinning, cracks, foreign particles of other disturbing lines of growth, and gaseous or liquid inclusions, is cut into plates which provide excellent control of frequency in broadcasting. The squares or rectangles are less than a millimeter in thickness and ordinarily on the order of 1 in. along each side. They are cut at definite angles with respect to the axes of the crystal, and ground with opposite surfaces parallel. Each small slab must be a section of one crystal, uniform throughout in atomic alignment. The thickness of the chip controls the frequency of a broadcast and it is most important to have the plates oriented and ground with utmost precision. Opposite surfaces are parallel to within 0.001 mm. and expansion or contraction due to the temperature is limited to one part in a million.

Jan 1, 1942

By C. K. Leith, W. J. NEAD

(Glen Summit Meeting, June, 1911.) . ONE Of the most significant developments in the iron industry in recent years has been the discovery and opening of enormous reserves of low-grade ore in eastern and northeastern Cuba. The two principal fields are the Mayari and the Moa, situated on Nipe bay, in the Province of Oriente. A less well-known district of the same type is that of Baracoa, at the east of the island, and another is in Camaguey province in central Cuba. In the comprehensive estimates of the iron-ore reserves of the world, published during the summer of 1910 by the International Geological Congress in Sweden,' these Cuban deposits are estimated at about 2,000,000,000 tons. Certain it is that the reserve is a large one. The Spanish-American Iron Co., the Juragua Iron Co. (Bethlehem Steel Co.), the U. S. Steel Corporation, and others have been active in this exploration.. The Spanish-American Iron Co. has established a port for the handling of these ores at Felton, has built a railway 16 miles to the ore-fields, and has opened up deposits for steam-shovel mining. Its expenditures have reached an aggregate of about $6,000,000 in preparation for the handling of these ores. Shipment of the ore to Sparrow's Point, Md., has begun and may be expected to rise to a considerable amount in the near future. The ore reaches this point at a cost per unit of iron considerably lower than Lake Superior ores, and the presence of a low percentage of nickel gives a desirable steel. It is not the purpose of this article to consider these ores from a commercial stand-point, but rather to discuss their-origin. If our conclusions are correct, they throw light on the character of the deposits which should have some commercial significance. 1 The Iron Ore Resources of the World, an inquiry made upon the initiative of the Executive Committee of the Eleventh International Geological Congress, Stockholm, vol. ii., p. 795 (1910).

Mar 1, 1911

By A. Lubinski, J. L. Logan, W. S. Althouse

A4ost gas twells and flowing oil wells are completed and treated through a string of tubing and a packer. Changes in temperature and in pressure inside or outside the tubing will: (I) if free motion of the tubing inside the packer is permitted, increase or decrease the length of the rubing; or (2) if free motion is prevented, induce forces in the tubing and on the packer. If pressure inside the tubing is greater than outside, the tubing may buckle helically even in the presence of a packer-to-tubing tension. The tubing will always buckle, and much more severely, if free motion is permitted. The buckling may be prevented by pulling the tubing in sufficient tension. The prediction of these forces and tubing movement has here to fore been based upon calculations that did not inciude helical buckling. This paper preseitts means with which these length or force changes can be calculated while taking into account the effect of helical buckling. To avoid damaging formations, failure of remedial operations, or damage to the tubing or packer, application is made to practical problems involving calculations of the required length of seals, amount of sluckoff or tension, and prevention of permanent corkscrewing. INTRODUCTION Leakage of a packer may result in costly failures of such operations as squeeze cementing, hydraulic fracturing, etc. To avoid such failures, the authors are often asked questions pertaining to the length of necessary seals, the amount of necessary slackoff, etc. Published work' does not take into account helical buckling of tubing. Investigation of helical buckling was prompted by the fact that allowance must be made for this phenomenon in order to provide relevant answers. In the past, theoretical work on helical buckling was confined to conditions for which such buckling does not The mathematical treatment of behavior in a buckled condition, given in the Appendix, is novel. Assumptions upon which this investigation is based are listed and discussed in a special section. The following are a few of the many kinds of problems which may be solved with this paper. 1. Consider a packer in which tubing may move. Such movement will occur after pressures and temperature are changed. The paper provides means for: (a) calculating the amount of such movement and, therefore. the required length of seals; and (b) calculating the necessary amount of initial slackoff, for which there is no danger of unsealing the packer, if the length of seals is given. Such calculations, as well as those which follow, tully take into account the fact that part of the movement ib due to elastic helical buckling of the lower part of the string. This buckling may occur even in tubing under tension. Insufficient initial slackoff for a given length of seals, or insufficient length of seals for a given slackoff, may result in costly failures. A field case of such a failure will be given further in this paper. 2. In the case in which tubing cannot move in the packer, changes of pressure and temperature result in tubing-to-packer forces and forces in the tubing above the packer, both of which may be calculated. This knowledge is important because, if these forces are too large, the) could damage the packer or the tubing. 3. For wells in which wireline tools are to be run through the tubing, the paper provides means to keep the tubing from buckling, thereby permitting free passage of tools. 4. In deep wells, mainly in the presence of large casing, tubing may become "corkscrewed", i.e., take a permanent helical set. A field case is described further in the text. Using this paper, one may calculate in advance conditions under which permanent corkscrewing would occur, and then take preventive steps. HELICAL BUCKLING Consider a string of tubing, freely suspended in the absence of any fluid inside casing, as shown in Fig. I(a). Now consider an upward force F applied at the lower end of this tubing. This force compresses the string; and if the compression is large enough (which is always the case in actual problems), the lower portion of the string will buckle into a helix, as shown in Fig. 1 (b). The lower end of the tubing is subjected to a compression F. This compression decreases with the distance from the bottom and becomes nil (neither compression nor ten-

By F. S. Pettit

The oxidation of Ni-3 to 25 wt pd Al alloys has been studied in 0. 1 atm of oxygen at temperatures between 900° and 1300°C. These alloys have been found to oxidize by three different mechanisms which depend on the temperature of- oxidation and the alloy composition. Two of the three mechanisms do not permit a continuous layer of Al,0, to be formed on the alloy surface and the oxidation rates are greater than that for pure nickel. The third mechanism results in the formation of an external A1203 scale and lke oxidation rates are about three orders of magnitude smaller than those for pure nickel. The minimum amount of aluminum required for the formation of external scales of A L,0, has been determined. NICKEL-base alloys are currently the main source of materials for use at elevated temperatures in gas turbine engines. These alloys are usually coated to obtain oxidation resistance. Coatings on nickel-base alloys are frequently formed by reaction of the alloy with aluminum whereby alloyed nickel aluminides are formed. The alloyed nickel aluminides provide protection to the nickel base alloy because external scales of A1203 (alumina) are formed during oxidation and mass transport through A120, is slow in comparison to mass transport through most other oxides. In view of the protective properties of A1203, it is important to know how much aluminum is required in these alloys in order to form external scales of AlzO,. The present paper is concerned with the oxidation kinetics and the oxidation mechanisms of Ni-A1 alloys and the minimum amount of aluminum required in these alloys for the formation of external scales of Alz03. THEORETICAL CONSIDERATIONS When a Ni-A1 alloy is heated in oxygen at elevated temperatures, the following reactions can take place on the surface of the alloy where the oxide phases are assumed to be virtually pure: These oxide phases are in the form of nuclei scattered over the surface of the alloy and, in view of their rapid formation, they need not be in equilibrium with the alloy. As the oxidation process continues, equilibrium between the alloy surface and the oxide phases is approached and the stability of the oxide nuclei is determined by the composition of the alloy at the alloy/oxide interface because of the following reactions: 3NiA1204 + 2A1 (alloy) = 4AlzO3 + 3Ni (alloy) [41 4Ni0 + 2Al (alloy) = NiA120, + 3Ni (alloy) [ 5 1 Application of the mass-action law to Eqs. [4J and [5J yields the following equilibrium conditions for these reactions: where aA1 and aNi are the activities of aluminum and nickel, are the standard free energies of formation of NiO, A1203, and NA1204, respectively, R is the gas constant, and T is the absolute temperature. If the composition of the alloy at the alloy/oxide interface is such that (akl/ahi) is greater than the equilibrium values defined by Eqs. [6] and [7], then Reactions (41 and [5] will go to the right as written. Conversely, if the alloy composition is such that the activity ratio (aLl,/aki) at the alloy/oxide interface is less than the equilibrium values, then Reactions [4] and [5] will proceed to the left. The equilibrium activity ratios in Eqs. [6] and 171 can be calculated since values for the standard free energies of formation of the oxide phases are available. Standard free energies of formation for NiO and A1203 have been tabulated by Elliott and ~leiser.' The standard free energy of formation for NiA1204 can be obtained from the data of Tretjakow and Schmalzried.' The results of these calculations are tabulated in Table I. Table I shows that the following inequality is valid over the temperature interval 900" to 1300°C: (Reaction [5]) (Reaction [4]) « 1and therefore the aluminum activity for these compositions can be taken as equal to the square root of the activity ratios (i.e., aNi = 1). If equilibrium is estab-

Jan 1, 1968