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President Mrs. Herman A. Prosser 1001 Park Avenue New York 28, N. Y First Vice-President Mrs. David E Park 115 East 67th Street New York 22, N Y. Second Vice-President Mrs Oliver Bowles 5000 Massachusetts Ave , N W. Wash 16, D C Third Vice-President Mrs. H Bobinson Plate 1215 Vancouver Avenue Burlingame, Calif

Jan 1, 1952

Executive ROBERT E. TALLY, Chairman WILLIAM H. BASSETT JOHN A. MATHEWS LOUIS S. CATES EDGAR RICKARD Finance H. A. GUESS HENRY KRUMB, Chairman H. G. MOULTON Admissions ERLE V. DAVELER, Chairman GEORGE D. BARRON H. K. MASTERS JOHN M. LOVEJOY P. A. MOSMAN Alternates E. L. ESTABROOK C. E. MEISSNER J. A. SINGMASTER FRED H. KAY

Jan 1, 1929

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-

Executive ROBERT E. TALLY, Chairman WILLIAM H BASSETT JOHN A. MATHEWS Louis S. CATER EDGAR RICHARD Finance HENRY KRUMB, Chairman H A GUESS H G. MOULTON Admissions ERLE V. DAVELER, Chairman GEORGE D BARRON H K MASTERS JOHN M. LOVEJOY P. A.-MOSMAN Alternates E. L. ESTABROOK C. E MEISSNER J. A. SINGMASTER FRED H. KAY

Jan 1, 1923

By Rossiter Raymond

(Butte Meeting, August, 1913.) ON Mar. 28, 1913, the Board of Directors of the American Institute of Mining Engineers unanimously adopted the following Minute: JOHN FRITZ, one of the most distinguished of American mechanical and metallurgical engineers, won that position by the force of innate genius, indomitable industry, unstained integrity and unfailing sympathy, and generosity towards his fellow-men. Self-educated in the hard school of practice, he appreciated nevertheless the advantages of technical instruction and discussion, and evinced this appreciation both by his membership and lively interest in this and other similar societies, and by his munificent gifts to engineering education at Lehigh University, and his long and faithful service us a Trustee of that institution. . As one of the foremost of those American engineers who, through their brilliant inventions and practical skill. developed here -the modern iron blast-furnace -and rolling-mill, and introduced and perfected the Bessemer process and other improvements in the manufacture of steel, Mr. Fritz contributed mightily to the chief departments of that industrial progress which characterized the Nineteenth Century. Proud of his great achievements, we cannot but rejoice over his long and fruitful life, crowned with a peaceful death ; but our praise and thanks are mingled with sorrow, as we recall the kindly face which we shall see no more on earth, and the loyal friendship and spontaneous good-will which led the love of his generation, and the reverence of the generation which followed, to regard him universally as " Uncle John Fritz." That. summary, though only an outline, is a good portrait ; and in the present sketch, we shall do no more than supply some details of the likeness, and some elements of the background.

Jan 6, 1913

By Cloyd M. Smith

A few years ago, the Ventilation Committee established the practice of resenting one topic each year for discussion at the annual meeting. The practice has met good response on the part of committee members and I suggest that it be continued. The topic chosen for this year, "Underground Anemometry," is a topic which has bothered me for more than 20 years. It seems to me that the coal industry is content to rely on slipshod methods for measuring the rate of flow of air underground, so I prefaced my discussional charge to committee members with the statement that I regard air measnrements made in the usual way, with hand held anemometer, as no good. Agreements and disagreements came in from more than a dozen engineers, some of whom are with operating companies, coal and metal; some with manufacturers; others with government agencies. The statement was accompanied by a questionnaire on the use of the rotating vane anemometer and by one describing two methods of using a mechanically held anemometer. The questionnaire will be considered first. The questionnaire and statement are as shown on pages 5 and 6, the committee members and respondents are given on page 4, and the general comments of the latter on page 5. Questionnaire 1. Has your company or agency issued written instructions for care and use of anemometers? If so, please enclose a copy with reply. Only one answer, McElroy's, was affirmative. It gave reference to Bureau of Mines publications1'5 which recom- mend the hand held anemometer for rough measurements and indicate that am accuracy of 5 pct can be had if calibration and method factors are used. Mathews said that instructions are principally oral while Maize reported that state inspectors of his department are well trained in use and care of anemometers. 2. Are your anemometers calibrated periodically? If so, by their manufacturer? or by? Are calibralion corrections applied to all observed mean velocity readings? Only one respondent, Lee, answered negatively as to calibration. This means that anemometers are generally calibrated but the questionnaire failed to ask how often this is done. As no one volunteered the information, we have no data on this point. In six cases the instruments are sent to their manufacturers for calibration. but Krickovic reports that his company limits manu-facturers' calibrations to anemometers which are used by operating personnel; those used by the engineering department being calibrated by U. S. Bureau of Standards. The Anaconda Copper Mining Co. has its ventilation engineers calibrate its anemometers. Most of the respondents say that a calibration correction is applied to each mean velocity reading, but Krickovic limits this to surveys made by the engineering department. Since Lee does not calibrate, he has no correction to apply. Maize reports that his department has its anemometers calibrated but does not apply corrections. 3. Do your men hold the anemometer by hand in measuring air flow? for 1 min? or traverse the section? for 1 min? or at? points for 5 sec each? Of 10 replies, 6 were "yes," 3 were "no," and one was "seldom" with respect to holding by hand. Among the six hand holders, four hold in a central position in the measuring section for a minute, except that two of them, Krickovic and Matthews, traverse the section by hand for survey or fan test. Their operating personnel hold by hand, centrally, for routine measurements. McElroy sometimes traverses with hand-held anemometer in rapid survey work. 4. If the anemometer is not held by hand, how is it supported? Augustadt supports the anemometer on an adjustable rod, Condon on "a rod of sufficient length to reach all points with observer standing in one position throughout traverse and at arm's length from plane of traverse." I presume that arm's length must be interpreted liberally enough to allow for arm movement, otherwise it would be impossible to manipulate the anemometer throughout the traverse section. Mancha upholds Condon in this method of traversing. Glanville hangs the anemometer on the end of a 4-ft staff by the hasp at the top of the anemometer frame. McElroy mounts it on the end of a rigid square shaft, 12 in. long, the staff being at right angles to the axis of the instrument. He traverses the section in two halves, holding the anemometer 3 feet from his body.

Jan 1, 1950

By P. F. Gnirk, J. B. Cheatham

The basic objective of this paper is to present a review of the state of knowledge concerning the fundamental mechanics of rock/bit-tooth interaction under downhole conditions. Of particular concern is the contributing significance of the various variables associated with the generation of rock chips by a single penetrating bit-tooth. The variables to be considered are fluid pressures which simulate borehole conditions, the mechanical properties of the rock, the shape and angle of attack of a bit-tooth, and the rate of load application on a bit-tooth. In addition, consideration is given to multiple bit-tooth penetration insofar as the effects of distance from and geometrical shape of adjacent penetration craters are concerned. Both experimental results and idealized theoretical models for single bit-tooth penetration are presented. Finally, the applicability of plasticity theory to drilling phenomena at depth, results of recent drag-bit studies, and several general theories of roller-bit drilling are briefly discussed. FUNDAMENTALS OF ROCK/BIT-TOOTH INTERACTION Drilling efficiency at depth in terms of penetration rate depends largely upon three essentially interdependent factors: 1) the bit, insofar as the mechanical motion, shape, and configuration of the bit-teeth are concerned; 2) the rock, as regards its mechanical behavior, or response to the penetrating action of the bit-teeth, when subjected to a state of stress induced by mud column, interstitial pore, and overburden pressure (and at great depths to high temperature) ; and

Jan 1, 1967

By F. H. Wilson, R. M. Brick

WITH the papers of Palmer and Smith1 and of Burghoff and Bohlen,2 published in 1942, understanding of the problem of the development of ears on deep-drawn brass cups was brought to the point where, from a practical standpoint, producers of brass sheet could keep earing under control. However, these very practical results raised questions concerning the reasons for the observed behavior. Since plastic deformation is fundamentally a function of crystallographic slip, these reasons must be considered in the light of the textures to be found in the annealed sheet. Various attempts have been made to interpret the mechanism of ear formation by correlation with the preferred orientation and the anisotropy of the sheet. However, none of these has satisfactorily explained why ears are usually found in the rolling and transverse directions for copper but at 45° to these directions for brass. This paper offers additional data on these two related subjects and has been divided into two sections. The first section provides a survey of the recrystallization textures of brass as affected by annealing temperatures and prior reductions, and an account of the earing behavior which accompanies these textures. The second section reports new data on the anisotropy that accompanies a characteristic texture for brass and endeavors with partial success to establish the factors that account for the difference in earing behavior between copper and brass. EARING BEHAVIOR OF BRASS Review of Textures The recrystallization texture of severely rolled brass was first reported by Bass and Glocker.3 The preferred orientation to which this texture, obtained from metal annealed at 500°C., was most akin was (113)[112]. This texture has been confirmed by Bauer, von Göler and Sachs;4 Brick;* Brick, Martin and Angier;6 and Cook and Richards7 who, in general, used annealing temperatures under 500°C. Bass and Glocker3 also reported the recrystallization texture at 850°C. to be the same as at 500°C. They analyzed their textures by means of single photograms obtained with white radiation. The photograms for both temperatures are reproduced in their paper, and there is a strong similarity between the two. However, for the latter temperature, the number of spots registered on the film was remarkably large for the grain size to be expected, and the authors made no mention of using a technique that would integrate a large enough area of the specimen to produce so many spots. The only other attempt to determine textures resulting from high temperature

Jan 1, 1945

By R. F. Mehl, C. S. Barrett, A. H. Geisler

THE mechanism by which the super-saturated solid solution of 20 per cent silver in aluminum decomposes has been reported in two previous publications. 1,2 The analysis of streaks in Laue photograms showed that thin platelike particles (the so-called Guinier-Preston aggregates) form upon {111} matrix planes in the early state of decomposition.1 The size of these particles is larger, the higher the temperature at which they form in accordance with nucleation theory;3 at all temperatures they increase in size with aging.2 When they have grown thick enough to afford three-dimensional diffraction, powder X-ray photograms show that the structure is not that of the equilibrium precipitate y but that of a transition lattice ?'. Since this is also platelike in shape and also lies upon the {111} matrix planes with the {110} direction in the matrix parallel to the {11.0} direction in ?', it seems likely that the original platelet particles are merely ?' in an early stage of formation, and thus finely dispersed. The atomic spacing and pattern on the {00.0} plane in ?' are identical with those on the {111} matrix plane to which it lies parallel, and since comparable directions in the two planes are parallel, the lattices are thus coherent at the interface; an analogous coherence has been found in aluminum-copper alloys.3 The structures ?' and y are both close-packed hexagonal and are oriented alike; they differ only in interatomic distances. Consequently, ? ' is regarded as y strained from its ordinary dimensions by the lattice coherency between it and the matrix.2 The lattice movements that transform the matrix to the equilibrium precipitate appear to be very simple.2 The mechanism of precipitation in this system is simpler and is more precisely known than that in any other system,2,4 hence the system should be a profitable one for the difficult task of correlating property changes with structural alterations. The present report provides additional studies on powder X-ray diffraction from alloys of 10 per cent, 20 per cent and 30 per cent Ag, and presents the correlation of crystallographic changes with changes in microstructure, Brinell hardness and electrical resistivity of the three alloys. PREPARATION OF SAMPLES AND EXPERIMENTAL PROCEDURE The preparation of the 20.2 per cent Ag alloy has been described.2 Alloys containing 9.9 and 29.7 per cent Ag were prepared from 99.97 per cent Al and 99.99+ per cent Ag using a similar procedure. Rolled

Jan 1, 1943

By R. E. Reed-Hill, W. H. Hartt

The "(3034) " twin lamellae in magnesium have been reexamined using electron microscope replicas. The double twinning sequence (1011)- (1012) for these lamellae has been reconfirmed. Evidence is presented showing that the irrational habit of these twins is probably the direct result of a need to accommodate the second-order twinning shear. This accommodation vesults in both an external shear in the matrix and an internal shear in the lamella. A model is presented which accounts for the experimental obseruations. HCP metals are generally characterized by strong textures in which the basal planes of the grains tend to be aligned parallel to the rolling direction in sheet or plate and to the axis of wires and rods. Since these directions are normally those in which finished products may be subjected to uniaxial tensile stress, these textures effectively place the crystals of magnesium objects in orientations unfavorable to both basal slip and {1012) twinning, the easily activated deformation systems of this metal. However, when magnesium crystals are deformed near room temperature by a tensile stress nearly parallel to the basal plane, another mode of deformation can occur.',2 This is _a double twin which forms first by twinning on {loll), followed by retwinning on (1012). The resulting twin lamellae are of considerable interest. First, they can be responsible for "brittle fracture''; when a tensile stress axis lies in the basal plane, because the reoriented crystal structure of a lamella is well-aligned for slip while the parent crystal is not. Extensive internal deformation may thus occur while the matrix is still almost undeformed. This deformation can produce a ductile rupture running the length of the twin.3 Complete failure of the specimen may then oc-cure by the spreading of cracks from one twin lamella to another, or by the movement of a crack into a grain boundary and then along grain boundaries. Since the the volume fraction of these doubly twinned elements is normally very small, the fracture may be classed as brittle, although the fracture mechanism is, of itself, essentially ductile. It is quite probable that the ductility transition, normally observed4 in magnesium at or slightly Obove room temperature, is closely associated with these second-order twins. The detailed relationship of these twins to fracture in single crystals will be the topic of another paper. The present paper is concerned with a second important aspect: the irrational habit of these double twins that falls close to {3034), or approximately 7 deg away from the primary (10il) twin habit. There is good reason to believe that this habit results directly

Jan 1, 1968

By D. C. Hilty, W. Crafts

The solubility of oxygen in iron containing aluminum has been determined at 1550°, 1600°, and 1650°C and found to be much higher than predicted from theoretical considerations, possibly due to equilibria with an iron-aluminum spinel phase rather than pure AI,O.. The presence of manganese greatly increased the deoxidizing power of aluminum. DEOXIDATION and inclusion formation in steel have proved to be elusive phenomena that are difficult to control in spite of much effort to understand and evaluate the reactions. Study of the problem indicated that more accurate data on the solubility of oxygen in iron containing deoxidizers were essential to further progress, and an empirical determination of oxygen solubilities has been initiated at the Union Carbide and Carbon Research Laboratories, Inc. The investigation has included the effects of aluminum, silicon, manganese, and combinations of these elements at 1550°, 1600°, and 1650°C. The equipment and experimental procedure as well as the results of a study of the effects of aluminum are described below. In general, it was found that the solubility of oxygen in iron containing aluminum is much higher than predicted, possibly because of the formation of complex nonmetallic phases, and that manganese greatly increases the deoxidizing power of aluminum. The generally accepted deoxidation curves for 1600°C are summarized in fig. 1, from "Basic Open Hearth Steelmaking"'. These curves are assumed to represent the solubility of oxygen in the presence of deoxidizers and should indicate the limits of mis-cibility gaps in the phase diagrams of the systems that control the formation and character of non-metallic inclusions as described by Benedicks and Lofquist'. They were derived mainly by application of the methods of thermodynamics to the available experimental observations, and by calculations based on the thermal constants of the pure substances when experimental data were lacking. Among the more notable researches contributing to the development of knowledge of oxygen solubilities are those of Korber and Oelsen8, 4, C. H. Herty, Jr. and associates5,6, Krings and Schackmann7, Went-rup and Hieber8 Schenck and Briiggeman9, Vacher and Hamilton'" and Chipman and co-authors 1,11,12,13 Practically, the deoxidation curves are of limited value in predicting oxygen content and rationalizing deoxidation practices. The reasons for this inadequacy appear to be error from inaccurate data, oversimplifying assumptions, interacting effects of combined deoxidizers, and possibly unknown extra-equilibrium and side reactions. Although inclusion formation is a very complex reaction it must be re-

Jan 1, 1951

By O. C. Holbrook, George G. Bernard

A new theoretical treatment has been obtained for the behavior of pattern waterflood injection wells when closed in. Two cases are treated: Case I where oil and water are assumed to have the same properties, and Case 2 where they arc different. In applying the method, one plots log (p — p,) vs closed-in time, where p is well-bore pressure at any tims and p, is static pressure. The value of p. is determined by trial and error as that value which makes the plot linear at large time. A value for the permeability-thickness product can be determined from the intercept of this linear part, and a value of the skin factor from the injection pressure at time of closing in. Application of the method to data from water floods at three fields seems to give reasonable results. For the case of unit mobility ratio, it is proved that this new method should give the same value for permeability-thickness product as the conventional pressure build-up method. In addition, the new method gives correct values for static pressure, whereas the conventional method does not, often indicating negative static pressures. The new method may be used in cases where the surface pressure persists after closing in as well as in cases where it does not. INTRODUCTION It is of considerable interest and importance to be able to determine the characteristics of the reservoir in an area surrounding a water injection well. Thus, if we can determine early in the life of an injection well that there is a considerable "skin effect", remedial measures can be started before a full-scale pattern flood begins. Similarly, if it can be shown that a gradual buildup of skin effect is occurring with time, measures to free the water of plugging material can be taken. Determination of static pressure in the water-injection well may show that the water is entering a thief zone and not the desired reservoir. Finally, determination of the permeability of the sand around the injection well will allow estimation of the future relation between injection pressure and rate. It should be possible to determine average reservoir permeability, skin effect and static pressure from pressure fall-off data. However, at the time we began work on this subject, it was thought that no adequate theory on which to base such determinations' was available. According to the conventional method which considers the reservoir to be filled with one fluid of small compressibility (see Van Everdingen, Joers2, and Nowak2), shut-in pressure is plotted vs log where is injection time, and At is closed-in time. The physical significance of injection time, may well be questioned in this case, since in a reservoir completely filled with a single fluid (as required by this theory) and with input and output rates equal, the pressure behavior after an initial transient is independent of t,. Attempts by our Tulsa area to use this theory led to negative values of static pressure in most cases. Because of these limitations of the method discussed above, it was decided to attempt to develop a new theory of pressure behavior in water injection wells, one which would apply when there is a gas saturation, as is so often the case in water floods. In the following treatment the assumptions and basic equations are given first, then the method of application of the equations. A complete example is given to clarify details of application. All difficult mathematics has been placed in the appendices so that the reader can follow the text without difficulty. However, if he wishes only to apply the results without knowing the basis for them, he can learn how to do this from reading only the sections entitled "Plotting of Experimental Results" and "Example." ASSUMPTIONS AND BASIC EQUATIONS Statement of Problem It will be assumed that a horizontal layer of constant thickness contains in its pore system a mixture of oil, gas and water. While water is being injected into this pore- system through a well at constant rate, an oil bank is built up, gas being expelled from the space taken by the oil as shown in Fig. 1. The saturations within each

C. G. Dunn (Generai! Electric Research Laboratory)— The author is to be commended on his attempt to calculate the residual strain energy from information on the dislocation density within the subgrains and a surface energy associated with the subgrains. However, much closer agreement between a calculated critical size of a nucleus and the observed size of grains that did not continue growing can be obtained if a reasonable correction is made in obtaining the energy of the surfaces of the subgrains. For example, since the sample is a single crystal with a cold-rolling reduction of 70 pct in thickness, one needs either an average disorientation for this or an average subgrain boundary energy rather than the 2.5 deg disorientation of a bent crystal, which was used by the author. From either the Laue photographs of the author or the pole density plot of Koh and Dunn 16 for a (113) [332] cold-rolled crystal the

Jan 1, 1961

By R. W. Raymond

[NoTE.—-This paper was presented at the Pittsburgh meeting in a partially completed form, and I fully expected to obtain, before the period of its publication, both the data and the leisure required for its completion. The hygiene of collieries was to have been separately considered, and the sanitary conditions of various metallurgical industries connected with mining were to receive an extended discussion, while at the same time the points treated in the paper as prosented at Pittsburgh were to have more ample illustration from American and European sources. Delay in obtaining expected information, and the continuous pressure of professional work, have prevented hitherto the execution of this plan ; and I can now publish only a portion of what I had designed to contribute to the subject. In the meantime this portion, but slightly changed, has been included as a chapter on the Hygiene of Metal Mines in a work entitled Hygiene and Public Health,, edited by Dr. A. H. Buck, of New York. An excellent chapter on the Hygiene of Coal Mines, contributed to the same work by Mr. Henry C. Sheafer, of Pottsville, affords me an opportunity to supply one of the deficiencies above alluded to. Mr. Shearer's chapter contains much material in the way of explanations not required by professional readers; And be moreover devotes a considerable space to the explosive gases, falls of roof, and other causes of accidents to life or limb—a branch of the subject not belonging strictly to bygiene. I therefore make extracts only from his treatise.—R. W. R ] It is convenient to divide mines, with reference to this subject, into two classes, collieries and metal-mines. Subterranean quarries, rock-salt mines, etc., present no conditions requiring them to be separated from the latter class.

Jan 1, 1880

By Martin F. Littmann

FOR magnetic devices employing reactors with high rates of flux change very thin magnetic tapes have been employed. One of the more interesting of

Jan 1, 1957

By David W. Pasho

The success of a collector vehicle, designed to recover manganese nodules under the conditions which exist in deep ocean mine sites will in part be determined by the effectiveness of pick-up and running gear mechanisms. For the purpose of qualitative comparison, some specific aspects of seafloor interactions with various concepts are reviewed utilizing existing data on seafloor characteristics and running gear/tool interaction with soils.

Jan 1, 1976

By E. Berl

THIS may be a most unnecessary paper-from what does crude oil come and how was it formed? Many people, inside and outside of the petroleum industry, believe that we have actually enough oil, and that we can easily produce very important products from this extremely valuable raw material. The writer believes, however, that the answer to this question concerning the parent material and the formation of oil is of broader interest, because it may be that from the answer to these problems it would be possible to get answers to other important indus-trial questions. Therefore, a study in this line seems to be justified, and the writer will submit some of the results which he has collected during more than ten years with many very capable collaborators, to whom his thanks may be expressed on this occasion.

Jan 1, 1938

By H. C. Theuerer

GeC14 may be purified by extraction with HCI and chlorine. The process is as effective for the removal of AsCI:, as the more cumbersome distillation methods usually used for this purpose. GERMANIUM for semiconductor use contains impurities at levels no higher than a few parts in ten million. Material of this quality is obtained from highly purified GeC1, by hydrolysis to the oxide and reduction of the oxide in hydrogen. When purifying GeCl,, AsC1, is the most difficult impurity to remove. This is usually accomplished by multiple distillation procedures.1-3 AsC1, may also be removed from GeC1, by extraction with HC1.1-4 Reducing the arsenic to low concentrations is not practicable, however, because of the large number of extractions needed. This paper discusses a new method for the removal of arsenic from GeC1, by extraction with HC1 and chlorine. The method is rapid, leads to little loss of germanium and is at least as efficient as the distillation procedures currently being used. Theory of Extraction Procedures In the simple extraction of GeC1, with HC1, the following reaction occurs ASCl8G8C1 D AsCl3rc1 at equilibrium CA/Cn= K, where K is the distribution coefficient, and C, and C,, are the molar concentrations of AsC13 in HC1 and GeCl,, respectively. The materials balance equation for this reaction is VACA + vncn = VnC,, where V, and Vn are the volumes of HC1 and GeCl4, respectively, and C, is the initial concentration of AsC13 in GeC1,. From this it can be shown that for multiple extractions where C,, is the concentration of AsC13 in GeC14 after n extractions, and r is the ratio of V, to V,,. It is assumed that r is maintained constant, that equilibrium is established during each extraction, and that K is independent of the AsCl3 concentration. By saturating the system with chlorine, the following reaction occurs in the aqueous phase AsCl3 + 4H2O + Cl2 D H5AsO4 + 5HC1 at equilibrium K' = ------------ ai - a4 h2u - aet2 where a is the activity of the various components. The effect of this reaction is to reduce the concentration of the AsC1, in the aqueous layer and, therefore, to promote further extraction of this component from the GeC1, layer. If the arsenic acid remains entirely in the aqueous phase, the net effect of this reaction is to promote the removal of arsenic from the GeC11. The materials balance equation for extraction with HC1 and chlorine with the foregoing reaction is, then, VaCC + VACA + VACn = VnCo where C,. is the molar concentration of H3AsO, in the HC1. With the added assumptions that the activities of AsC13 and H8ASO4 in the aqueous phase are equal to their molar concentrations, it can be shown that for n extractions Cn/Cu = (1/rkK + rK + 1) n where k - K1 a4h2o - acl2/aoncl. It can be seen by comparing Eqs. 1 and 2 that if k is large, the removal of AsC1, by HC1 extraction will be greatly improved by the addition of chlorine. Dilution of the HCI used in the extraction with chlorine would also favor the separation. This, however, would increase the loss of GeCl,, which is undesirable. Experimental Procedure Germanium prepared from oxide of semiconductor purity is n-type with resistivities greater than one ohm-cm. The resistivity is controlled by the donor concentration, which is —lo-: mol pct. Germanium prepared from material with added arsenic will have lower resistivity commensurate with the arsenic concentration. With such material, at arsenic concentrations above 10-1 mol pct the resistivity is controlled by the added arsenic, and effects due to other impurities initially in the oxide are negligible. In this investigation GeO, of semiconductor purity was converted to GeCl,, and -0.01 mol pct As was added. This material was used for the extraction experiments and the purification attained determined by a comparison of the resistivity data for samples of germanium prepared from the initial and purified GeC1,. A method for calculating the arsenic concentration from the resistivity data is discussed later. The details of the experimental procedures used are as follows: Two hundred and thirty cu cm GeC1, were prepared by the solution of GeO, in HC1, followed by

Jan 1, 1957

By Maurice C. Fetzer, Charles R. Austin

It has long been known that plain high-carbon steels may be susceptible to graphiti-zation below the A1 critical, but no data have been available to indicate what factors cause and tend to inhibit graphite formation. Two recent publicationsl,2 have shown that the factors controlling graphitization below the A1 are different from those operating above the A1 inversion where commercial graphitization of malleable iron begins. Furthermore, for plain high-carbon steels graphitization below the critical point does not appear to be related to ordinary chemical analyses. Many years ago it was recorded3 that the rate of graphitization at subeutectoid temperature is not a maximum just below the A1 critical, but at some lower temperature, which Austin and Norris have shown to be about 670°C. Indeed, work done in our laboratory has demonstrated that it is impossible to spheroidize certain steels in the temperature range of 650° to 710°C. without the formation of considerable amounts of graphite. However, if the temperature is maintained just below the A1 (720°C.) these same steels may be completely sphe-roidized at constant temperature. In previous studiesl,2,4 on I per cent plain carbon steels graphitization was encountered during prolonged tempering. The limited number of steels studied did not provide sufficiellt data to permit adequate study of the factors controlling this graphitization. Accordingly, a limited statistical investigation was undertaken, utilizing 18 steels of similar chemical analyses, furnished by four steel companies, who also supplied information regarding the history of manufacture. An extensive program of research is being carried out on these steels, including the effect of pretreatment and atmosphere on the nature and extent of graphitization, and the possible correlation of graphitization with such characteristic properties as hardenability, grain size and mechanical behavior. In the present paper discussion is restricted to a study of the correlation between graphitizing tendency at 670°C. after quenching from several temperatures above the critical, and (I) the minor variations in the chemistry of these steels of "similar" chemical composition, and (2) the deoxida-tion practice employed. The state of the lead bath, oxidized or protected from oxidation by charcoal, used in the tempering treatments is also considered. Materials Eighteen plain carbon steels of about I per cent carbon, and containing similar amounts of each of the other common elements usually found as impurities, were obtained in the form of rods % in, in diameter from four steel manufacturers. The analyses for ordinary and special elements of all the steels were made on the rod stock as received in the laboratory, and the re-

Jan 1, 1941

By Maurice C. Fetzer, Charles R. Austin

It has long been known that plain high-carbon steels may be susceptible to graphiti-zation below the A1 critical, but no data have been available to indicate what factors cause and tend to inhibit graphite formation. Two recent publicationsl,2 have shown that the factors controlling graphitization below the A1 are different from those operating above the A1 inversion where commercial graphitization of malleable iron begins. Furthermore, for plain high-carbon steels graphitization below the critical point does not appear to be related to ordinary chemical analyses. Many years ago it was recorded3 that the rate of graphitization at subeutectoid temperature is not a maximum just below the A1 critical, but at some lower temperature, which Austin and Norris have shown to be about 670°C. Indeed, work done in our laboratory has demonstrated that it is impossible to spheroidize certain steels in the temperature range of 650° to 710°C. without the formation of considerable amounts of graphite. However, if the temperature is maintained just below the A1 (720°C.) these same steels may be completely sphe-roidized at constant temperature. In previous studiesl,2,4 on I per cent plain carbon steels graphitization was encountered during prolonged tempering. The limited number of steels studied did not provide sufficiellt data to permit adequate study of the factors controlling this graphitization. Accordingly, a limited statistical investigation was undertaken, utilizing 18 steels of similar chemical analyses, furnished by four steel companies, who also supplied information regarding the history of manufacture. An extensive program of research is being carried out on these steels, including the effect of pretreatment and atmosphere on the nature and extent of graphitization, and the possible correlation of graphitization with such characteristic properties as hardenability, grain size and mechanical behavior. In the present paper discussion is restricted to a study of the correlation between graphitizing tendency at 670°C. after quenching from several temperatures above the critical, and (I) the minor variations in the chemistry of these steels of "similar" chemical composition, and (2) the deoxida-tion practice employed. The state of the lead bath, oxidized or protected from oxidation by charcoal, used in the tempering treatments is also considered. Materials Eighteen plain carbon steels of about I per cent carbon, and containing similar amounts of each of the other common elements usually found as impurities, were obtained in the form of rods % in, in diameter from four steel manufacturers. The analyses for ordinary and special elements of all the steels were made on the rod stock as received in the laboratory, and the re-

Jan 1, 1941