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Part IX – September 1968 - Papers - Enhanced Ductility in Binary Chromium AlloysBy William D. Klopp, Joseph R. Stephens
A substantial reduction in the 300°F ductile-to-brittle transition temperature for unalloyed chromium was achieved in alloys from systems which resemble the Cr-Re system. These alloy systems include Cr-Ru, Cr-Co, and Cr-Fe. Transition temperatures ranged from -300° F for Cr-35 at. pct Re to -75°F for 0-50 at. pct Fe. The ductile alloys have high grain gvowth rates at elevated temperatures. Also, Cr-24 at. pct Ru exhibited enhanced tensile ductility at elevated temperatures, characteristic of superplas-ticity. It is concluded that phase relations play an importarlt role in the rhenium ductilizing effect. The ductile alloys have compositions near the solubility limit in systems with a high terminal solubility and which contain an intermediate o phase. The importance of enhanced high-temperature ductility to the rhenium ductilizing effect is not well understood although both may have common basic features. CHROMIUM alloys are currently being investigated for advanced air-breathing engine applications, primarily as turbine buckets and/or stator vanes. The inherent advantages of chromium as a high-temperature structural material are well-known1 and include its high melting point relative to superalloys, moderately high modulus of elasticity, low density, good thermal shock resistance, and superior oxidation resistance as compared to the other refractory metals. Additionally, it is capable of being strengthened by conventional alloying techniques. The major disadvantage of chromium is its poor ductility at ambient temperatures, a problem which it shares with the other two Group VI-A metals, molybdenum and tungsten. For chromium, the problem is further amplified by its susceptibility to nitrogen em-brittlement during high-temperature air exposure. In cases of severe nitrogen embrittlement, the ductile-to-brittle transition temperature might exceed the steady-state operating temperature of the component. The low ductility of chromium would make stator vanes and turbine buckets prone to foreign object damage. The present work was directed towards improvement of the ductility of chromium through alloying, with the anticipation that any improvements so obtained might be additive to strengthening improvements achieved through different types of alloying. The alloying additions for ductility were selected on the basis of the similarity of their phase relations with chromium to that of Cr-Re. The reduction in the ductile-to-brittle transition temperatures of the Group VI-A metals as a result of alloying with 25 to 35 pct Re is well established.a4 the temperature range -300" to 750° F. This phenomenon is commonly referred to as the '<rhenium ductilizing effect"; this term is also used to describe systems in which the ductilizing element is not rhenium. Other alloy systems which have recently been shown to exhibit the rhenium ductilizing effect include Cr-Co and c-Ru.= In order to explore the generality of this effect, alloys were selected from systems having phase relations similar to that of Cr-Re, primarily a high solubility in chromium and an intermediate o phase. The following compositions were prepared: Cr-35 and -40Re; Cr-10, -15, -18, -21, -24, and -27 pct Ru; Cr-25 and -30 pct Co; Cr-30, -40, and -50 pct Fe; Cr-45, -55, and -65 pct Mn. Seven other systems were also studied which partially resemble Cr-Re. These systems have extensive chromium solid solutions or a complex intermediate phase, not necessarily o. The compositions evaluated include the following: Cr-20 pct Ti; Cr-15, -30, and -45 pct V; Cr-2.5 pct Cb; Cr-2.5 pct Ta; Cr-20 pct Ni; Cr-6, -9, -12, and -15 pct 0s; Cr-10 pct Ir. The compositions of alloys in these systems were chosen near the solubility limit for the chromium-base solid solutions, since in the Group VI-A Re systems, the saturated alloys are the most ductile. These alloys were evaluated on the basis of hardness, fabricability, and ductile-to-brittle transition temperatures. In addition to the studies of alloying effects on ductility, an exploratory investigation was conducted on mechanical properties at high temperatures in Cr-Ru alloys EXPERIMENTAL PROCEDURE High-purity chromium prepared by the iodide deposition process was employed for all studies. An analysis of this chromium is given in Table I. Alloying elements were obtained in the following forms: Commercially pure powder — iridium, osmium, rhenium, and ruthenium. Arc-melted ingot — titanium and vanadium. Electrolytic flake — iron, manganese, and nickel. Sheet rolled from electron-bearn-melted ingot — columbium and tantalum. Electron-beam-melted ingot — cobalt. Sheet rolled from arc-melted ingot — rhenium. All alloys were initially consolidated by triple arc melting into 60-g button ingots on a water-cooled hearth using a nonconsumable tungsten electrode. The melting atmosphere was Ti-gettered Ar at a pressure of 20 torr. The ingots were drop cast into rectangular slabs and fabricated by heating at 1470" to 2800° F in argon followed by rolling in air. Bend specimens measuring 0.3 by 0.9 in. were cut from the 0.035-in. sheet parallel to the rolling direction. The specimens were annealed for 1 hr in argon, furnace cooled or water quenched, and electropolished prior to testing. Three-point loading bend tests were conducted at a crosshead speed of l-in. per min over
Jan 1, 1969
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Institute of Metals Division - The Tensile Fracture of Ductile MetalsBy H. C. Rogers
A phenomenological study of the failure of polycry stalline ductile metals at room temperature was carried out using light and electron microscopy. Tensile fractures as well as sections of partially fractured bars of OFHC copper in particular were examined. The initiation and growth of the central crack in the neck of a tensile specimen occurs by void formation. After the formation of the central crack the f'racture may be completed in either of two ways: by further void formation or by an "allernating slip" mechanism. The first leads to a "cup-cone" failure; the second, to a "double-cup" failure. In the past decade or decade and a half there has been a great deal of emphasis on the solution of the problem of the brittle fracture of metals, particularly those which normally exhibit considerable ductility such as steel. Since the problem of the fracture of metals after large plastic strains has less immediate commercial or defense significance, there has been considerably less effort expended in describing the details of the phenomenology and determining the mechanism of this type of fracture. The present research was undertaken to increase our knowledge in this area. The problem of ductile fracture has not been neglected completely, however. Ludwik1 first found by sectioning a necked but unbroken tensile specimen of aluminum that fracture began with a large internal crack which appeared to have started in the center of the neck. Examination of the fracture indicated that the crack had propagated radially with increasing deformation until a point was reached at which the path of the fracture suddenly left this transverse plane and proceeded at approximately 45 deg to the stress axis until the surface was reached. This gives rise to the commonly observed cup-cone tensile fracture. When MacGregor2 was attempting to demonstrate the linearity of the true stress-true strain curve from necking until fracture, he found that copper was anomalous in that the stress dropped off markedly from the straight line value before fracture occurred. Radiography indicated that in the copper an internal crack was formed long before the final fracture, the stress decreasing during the growth of this crack. One of the most significant advances in the understanding of ductile fracture was the result of work by Parker, Flanigan, and Davis.3 By the use of etch-pit orientations they were able to demonstrate conclusively that the fracture surface at the bottom of the cup, although on a gross scale normal to the tensile axis, did not consist of cleavage facets as had been previously supposed by many investigators. Recently, Forscher4 has shown evidence of porosity near the tensile fracture of hydrogenated zirconium which he attributes to hydride decomposition. The workers at the Titanium Metallurgical Laboratory5 have also shown evidence of porosity in a number of the commonly used metals after heavy deformation. Many metals have relatively low ductility during creep tests at high temperature. The fractures are intercrystalline, resulting from the nucleation and growth of grain boundary voids. The work in this area has been recently reviewed by Davies and Dennison.6 It is possible that some of the observations and conclusions may have a bearing on the present study? especially since at least two studies7,' have been extended down to room temperature and below using magnesium alloys. However, since magnesium does exhibit low-temperature cleavage, these results may not be pertinent to the present one. The use of the electron microscope as an aid to the study of fractures has been extensively exploited by Crussard and coworkers.9 The examination of direct carbon replicas of the fractures of a large number of metals and alloys showed that the bulk of the fracture surface was covered with cup-like indentations of the order of 1 to 2 µ in size. These frequently had a directionality by which Crussard claims to be able to tell the direction of the crack propagation. With this rather disconnected background of information, this investigation was undertaken in the hope of presenting a unified picture of the initiation and propagation of a fracture in a ductile metal. To this end all of the techniques previously used were employed simultaneously so that there might be a good correlation of the data obtained by different techniques. EXPERIMENTAL PROCEDURE The metal which was chosen as the starting material for this investigation was OFHC copper. Of the dozen or so materials considered, it best fulfilled the requirements of commercial availability in large sizes, good ductility, relatively high melting point compared with room temperature and
Jan 1, 1961
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Part VII - The Effect of Temperature on the Dihedral Angle in Some Aluminum AlloysBy J. A. Bailey, J. H. Tundermann
The dihedral angles of the solid-liquid interfaces were measured at various temperatures above the solidus and the interfacial energies calculated when small additions of copper, indium, lithium, magnesium, antimony, and silicon were made to an aluminum alloy containing 3 pct Sn. When the results were compared with those of the Al-Sn alloy some differences were found which could be interpreted in terms of the ability of the added element to enter into solution or form intermetallic compounds with the aluminum and tin. It was shown that in some cases considerable changes in the shape of intergvanular liquid films can be brought about by comparatively small compositional changes in the alloy. DURING the melting or solidification of an alloy a temperature range is usually found where the presence of a liquid phase may be detected at the grain boundaries of a solid. It is believed that the presence of this liquid phase is responsible for hot tearing in castings and welds and hot shortness in the working of some alloys at elevated temperatures. Rosenberg, Flemings, and Taylor1 in a study of the solidification of aluminum castings have indicated the importance of intergranular liquid films and shown that their shape and distribution at the end of solidification effect the hot tearing characteristics of the material. The shape of such intergranular liquid films are determined largely by the ratio between the solid-liquid interfacial energy (yLS) and the grain boundary energy (ySS). A measure of this ratio (yLS/ySS , relative interfacial energy) is the dihedral angle 8. The dihedral angle 0 is related to the relative interfacial energy by the following expression: Rogerson and Borland 2 have also suggested that the shape of the intergranular liquid is an important factor in determining the susceptibility of a material to hot shortness. They showed that on a comparative basis materials having the lowest dihedral angles at a given temperature gave the greatest severity of cracking. They stated that liquid in the form of globules should be less harmful than liquid in the form of extensive films as more intergranular cohesion should be possible. Rogerson and Borlland 2 also showed that the susceptibility of an A1-Sn alloy to hot cracking can be reduced by small additions of cad- mium. It was found that the cadmium gave an increase in the dihedral angle at all temperatures. Ikeuye and smith3 investigated changes in the dihedral angle and relative interfacial energy with temperature for a number of ternary alloys formed when small additions of bismuth, cadmium, copper, lead, and zinc were made to an A1-Sn alloy. They found that in most instances changes in the dihedral angle were caused by compositional changes in the liquid phase; as the composition of the liquid approached that of the solid the dihedral angle decreased. They noted that the addition of a third element which was soluble in both the liquid and solid phases at a given temperature may decrease the dihedral angle (e.g., the addition of copper or zinc) but otherwise the ternary alloys formed exhibited dihedral angles between those of the A1-Sn binary alloy and those of the binary alloy of aluminum with the added element. Dwarakadasa and Krishnan4 investigated the changes in dihedral angle and relative interfacial energy with temperature when small additions of magnesium, iron, silicon, manganese, sulfur, cobalt, and silver were made to a copper alloy containing 3 pct Bi. They found that in all cases the added elements gave an increase in the dihedral angle and relative interfacial energy when compared with the values obtained for the simple binary alloy at the same temperature. It was noted that an increase in temperature gave a decrease in dihedral angle and relative interfacial energy in each of the ternary alloys studied. Similar results have been obtained by Ramachandran and Krishnan5 for the addition of small quantities of lead. This paper describes the application of dihedral angle measurement to the determination of the shapes of liquid phases at various temperatures above the solidus when small additions of copper, indium, magnesium, lithium, antimony, and silicon are made to an aluminum alloy containing nominally 3 pct Sn. An attempt is made to correlate the measurements with the relative solubility of the added elements in tin and aluminum. The work was undertaken to provide more data concerning the effects of temperature and composition on the shape of liquid films above the solidus. EXPERIMENTAL PROCEDURE In the present work ternary aluminum alloys containing nominally 3 pct Sn and small additions of high-purity copper, indium, lithium, magnesium, antimony, and silicon were made. The alloys were melted in a graphite crucible under an inert atmosphere of argon and cast into ingots 6 in. long by 0.5 in. diam. The ingots were then cut into rods 1.5 in. long, given a 50 pct cold reduction, and machined into test pieces 0.5 in. long by 0.5 in, diam for heat treatment. The alloy samples were annealed at the various test temperatures between the liquidus and solidus for approxi-
Jan 1, 1967
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Industrial Minerals - Measurement of Cement Kiln Shell Temperatures (Mining Engineering, Feb 1960, pg 164)By R. E. Boehler, N. C. Ludwig
At Buffington Station, Gary, Ind., Universal Atlas Cement operates fourteen 8 x 101/2 x 155-ft cement kilns in mill 6 and two 11 x 360-ft kilns in the Harbor plant. The No. 11 and 12 kilns in mill 6 are equipped with Manitowac recuperator sections. This report describes studies in measuring exterior shell temperatures on several of these kilns and the development of a traveling radiation pyrometer with certain novel features. Preliminary Work: At first various temperature-sensing devices were placed on the steel shell: 1) crayons with calibrated melting points, 2) colored paints with temperature-calibrated pigments, 3) aluminum paints with temperature-calibrated binders, and 4) metal-stem dial thermometers. The colored paints and aluminum paints failed to indicate the temperatures correctly. The crayons and thermometers did indicate fairly correct temperatures, but it proved impossible to apply enough of these on the shell to detect all the potential areas where hot spots might develop. Furthermore, considerable labor was required to apply these sensors and read the temperatures. Consequently no further work was done with these devices. Formation of Hot Spots: In the burning or clinker-ing zone of a cement kiln, the thickness of the protective coating and thickness of the brick govern the amount of heat transmitted to the steel kiln shell. Usually the protective coating consists of 4 to 8 in. of fused cement clinker. The formation of a hot spot is usually caused by loss of coating? that is, localized areas of the coating become thin or fall away from the refractory. This is generally caused by excessive temperature in the burning zone over a fairly long period of time. It may also be caused by a sudden thermal change in the burning zone. Variations in raw feed composition and in feed rate require changes in the fuel and air rates, and when these are not appropriately altered, conditions may develop in the kiln that will result in loss of coating. Luminescence on the kiln shell indicates that a hot spot has developed to a point that usually alters the refractory's thermal conductivity properties. When this thermal weakness zone occurs in the burning zone of the kiln, constant vigilance is required to protect it by maintaining proper coating. Even so, it has been the writers' experience that within a period of several days to about four weeks the hot spot usually recurs with greater severity. This necessitates shutting down the kiln and re-bricking the affected area. One of the prerequisites of a good burnerman is the ability to maintain a protective coating despite the many variables in operation. When he knows that it is getting thin or that an area has dropped off, he reduces the firing rate and kiln speed and brings feed into the affected area in an effort to rebuild the coating. But when powdered fuel is burned, the atmosphere of the kiln may prevent the burnerman's observing the condition of the coating closely at all times without taking off the fire. It is not considered good practice to do this frequently, as it imposes a thermal shock on the coating and upsets operation of the kiln. To help the burnerman scan the shell of the kiln along the burning zone, therefore, a radiation pyrometer, connected to a potentiometric recorder, was mounted on a slowly moving steel cable. The theory of operation, construction details, and adaptability of the radiation pyrometer are included in an excellent monograph' and also in a textbook.' Shell temperatures of the Atlas Cement kilns were measured with a Brown Instruments Div. low intermediate range Radiamatic unit, of range 200" to 1200°F, and a circular chart Electronik potentio-metric recorder, of range 500" to 1000°F. In Bulletin 59095M the supplier publishes standard calibration data (millivolts vs degrees Fahrenheit) for this radiation pyrometer, These data, however, apply only to flat surfaces having emissivities of unity. Calibration of Radiation Pyrometer for Use on Curved Surfaces: When applied to surface temperature measurements, the radiation pyrometer reading depends on the nature of the surface, the material of which it is composed, and also to some extent on the temperature of the surroundings. Although the present radiation pyrometer is designed to give a calibrated response under ideal (black body) conditions when used commercially, it must be calibrated empirically. The calibration procedure, given below, follows that described by Dike (Ref. 1, pp. 38-39). Calibration tests on plane and curved surfaces showed that the response of the radiation pyrometer was very
Jan 1, 1961
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The Effect of Silver on the Chlorination and Bromination of GoldBy T. KIRKE ROSE
A Discussion of the paper by H. O. Hofman and M. G. Magnuson, read at the Lake Superior meeting, September, 1904. (British Columbia Meeting, July, 1905.) T. KIRKE ROSE, London, Eng. (communication to the Secretary*`) :-The authors have shown that, under certain conditions, the rate of dissolution of gold by chlorine and bromine is re¬duced by the addition of 10 per cent. of silver to the gold, and that the action is almost stopped when the silver amounts to 30 or 40 per cent. of the alloy. Even if full recognition is given to the practical way in which the work was done, how¬ever, it is to be regretted that Prof. Hofman and Mr. Magnuson did not determine the temperature at which the experiments were carried out. From the details given it may be inferred that the temperature was raised by chemical action by about 20° C. when 21 g. of sulphuric acid were added, and that the mixture was then slowly cooled down during the experiment. When bromine or very weak chlorine solutions were used, there could not have been any perceptible heating action. As the action of both chlorine and bromine is aided by heat, it follows that the stronger solutions of chlorine were given an unfair advantage over the weaker solutions and over bromine. If the temperature had been the same in each case, I do not think that the conclusions given oil p. 432 of the Bi-Monthly Bulletin, March, 1905, 1 would have been found to be justified. (This is speaking generally. In barrel-treatment the conditions are similar to those in the experiments.) The superior speed of bromine as compared with chlorine at equivalent strengths is not yet disproved, and the differences noted between strong and weak solutions of chlorine may have been largely a function of the temperature. Moreover, the authors used somewhat coarse particles of gold
Sep 1, 1905
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Petroleum Division Plans Two Fall MeetingsBy AIME AIME
THE Petroleum Division will hold two meetings this fall, one on the Coast at Los Angeles, Sept. 29, with the technical sessions in the assembly room of the California Oil and Gas Association and a banquet Friday evening at the Richfield Cafe atop the Richfield building; the other in the Southwest, at Dallas, Texas, Oct. 6 and 7, with the Baker Hotel as headquarters. Dr. Frederick M. Becket, President of the Institute, and A. B. Parsons, Secretary, will attend both meetings. Arrangements for the meetings are not yet complete but the respective local committees, working in close touch with the officials of the Division are rapidly shaping up the programs and other detail.
Jan 1, 1933
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How Engineers are Ferreting out Jobs in New YorkBy AIME AIME
THE Employment Bureau of the F. A: E. S., conducted under- the direct supervision of the secretaries of the four Founder Societies, has wanted to extend its activities and usefulness but it is operating right up to the limit of its budget; consequently, anything which requires the expenditure of more funds cannot be -undertaken, for the present. A great deal of time has been spent in recording, classifying, and interviewing the men listed, but owing to the business depression, only a comparatively small number of men have been placed' luring the last few months. There are men in New York from all over the country. What the Bureau needs is more positions available. With this in view, a number of high-grade engineers, themselves in need of employment, volunteered their services for a publicity campaign in the City of New York. A definite mode of procedure was evolved, and the success of the movement has been considerable, so much so that it has been thought well to call it to the attention, of members elsewhere, so that similar committees ' and campaigns might be organized in other cities. Following is a chronological arrangement of the methods used.
Jan 1, 1921
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An Improvement in ClassifiersBy AIME AIME
AN entirely new type of classifier is being put on the market by The Dorr Co., following three years of development and the experimental use of thirty machines of the improvement design in various parts of the world. It is known as the Multizone classifier. Compared with the older type the lower or overflow end has been decked over and is surmounted by one or more circular overflow columns. Feed is introduced near the middle of the machine and passes downward and under a vertical baffle, then along the underside of the deck to the base of the overflow columns. Under the baffle there is a restricted turbulent zone of high pulp velocity which holds the fine and critical size particles in suspension, preventing
Jan 1, 1937
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Oil and Gas Development in the Texas Panhandle, 1945By H. W. McCue
In 1945 the number of oil wells drilled was less than in 1944 but the number of gas wells was greater. The oil wells numbered 176, completed for an initial production of 25,214 bbl., an average of 143 bbl. per well as against a total in 1944 of 245 drilled for 32,886 bbl., or 134 bbl. per well. All of these wells were in proven areas and no new discoveries
Jan 1, 1946
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The Drift Of Things (8aa7aff5-f216-44e7-8c90-ae26f72cbad9)By Edward H. Robie
MANY engineers currently are working harder than usual, in part because of the demands being made upon them for increased production in the war effort, and in part because engineers are in short supply so that there is more to do for those who are available. In some instances the question has come up as to what additional payment, if any, should properly be made for overtime work, and to what extent is such payment legally permitted under the rules of the Salary Stabilization Board. Most engineers employed in an executive, administrative, or outside salesman capacity are not paid for overtime. They are paid for doing a job instead of for the hours they put in, and are free to do all the unpaid home work they feel they should do after dinner, as well as to do a bit of thinking and worrying during wakeful hours in bed. But engineers employed in a strictly professional capacity normally have standard office hours. Some employers pay for overtime and some don't. Their practice as it existed on Jan. 25, 1951 may be continued. In the absence of such practice at that time, the Salary Stabilization Board says that the engineer may now receive additional compensation up to his straight-time rate for an extended work week. No formal approval of the Board is required. "A professional engineer," in the mind of the Board, "is a person employed in a professional capacity, who, by reason of his special knowledge of the mathematical and physical sciences and the principles and methods of engineering analysis and design, acquired by professional education and practical experience, is qualified to practice engineering." Inducted Engineers A letter from a young man just inducted into the service and fearful that his engineering training is not going to be utilized reached us last week from Fort Riley, Kan. The AIME, cooperating with the other Founder Societies, is doing what it can, through the Engineering Manpower Commission, to see that engineers are not being wasted in the military establishment. So we passed this young man's letter along to T. A. Marshall Jr., executive secretary of that Commission. Mr. Marshall tells us that the normal procedure now being followed by the Army in handling Selective Service inductees is to have them first complete 16 weeks of basic training before assignment to specialized categories. During that time they are classified. If one has an engineering degree he should be classified as scientific and engineering personnel at the end of the basic training period. He should then be transferred to a technical detachment and assigned an MOS (Military Occupational Specialties) reflecting his education. If a young man is looking for a commission, it might be added that the current policy in the Army is to transfer to OCS (Officer Candidate School) applicants for commissions in the infantry only. The local unit commander can give information on this point, based upon the aptitude shown in tests. In view of the current shortage of engineers, it is believed that a young man should seriously consider remaining in enlisted status unless he can obtain a commission in a branch of the service that can make full use of his technical skills. His work may thus be more to his liking even if his uniform is not. New York or Atlantic City? In which place is it preferable to hold the annual meeting of a professional society like the AIME-New York or Atlantic City? That is, a winter meeting. The American Society of Mechanical Engineers has held its recent meetings at Atlantic City, with increasing attendance and satisfaction. The American Institute of Chemical Engineers chose Atlantic City for its recent December annual meeting. Only twice has the AIME ever met in this famous seashore resort: in 1898 and 1904. Chief advantages of going to Atlantic City over New York are that technical sessions are better attended, there being little else to do there in Winter; the cost to members is less, and hotel facilities are better adapted to a large meeting. As to cost, take a banquet, for instance. The Chalfonte-Haddon Hall, which caters especially to winter conventions, charges about $7 for a banquet dinner of standard quality. A similar dinner at the Statler in New York would cost about $8.50, and about $10.50 at the Waldorf-Astoria. (The charge for tickets is somewhat greater than this because of the cost of music, programs, flowers, and other incidentals.) Rooms, too, are somewhat less at Atlantic City, two in a room being accommodated for about $7 per day each, compared with $7 to $10 at a headquarters hotel in New York. On the other hand, AIME headquarters is put to some extra expense for staff travel, food and lodging, and members living in New York and environs are forced to pay a hotel bill. New York, of course, has more varied amusements to offer, plenty of big stores, and the glamour of a big city. The choice may be discussed at the forthcoming meeting in New York. In the meantime if any reader cares to express an opinion one way or the other we shall be glad to hear it. College Scholarships Most parents of children in the later stages of high school find it necessary to give some consideration to the cost of a college education. Although salaries have increased substantially it seems that the cost of the necessities of life, such as food, housing, and maintaining the family automobile, have gone up even more, so the problem of financing the children's education is as acute as ever. Many overlook the possibility of scholarships, or feel that only a student at or near the top of his class has a chance to get one. As a matter of fact, close to 150,000 scholarships and more than 15,000 fellowships, worth some $42,000,000, are available in 1200 American colleges and universities. Those who are interested should send 55¢ to the Superintendent of Documents, Government Printing Office, Washington 25, D. C. for a 248-page publication just issued by the U. S. Office of Education, entitled "Scholarships and Fellowships Available at Institutions of Higher Education."
Jan 1, 1952
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Part VII – July 1968 - Papers - The Charpy Impact Behavior of AI3Ni Whisker-Reinforced AluminumBy F. D. George, M. J. Salkind
Al3Ni whisker-reinforced aluminum was found to exhibit good Charpy impact toughness and little notch sensitivity even though its room-temperature tensile elongation parallel to the whiskers is only 2 pct. This impact behavior was maintained d liquid nitrogen temperature (-196"C). It is postulated that this behavior is due primarily to the presence of the continuous aluminum matrix which provides sufficient 10calized ductility in the vicinity of the crack tip to absorb considerable energy from the advancing crack. The impact behavior of Al-Alni was found to be quite anisotropic. Of six orientations studied, the transverse orientation having the notch normal to the whisker axis was found to exhibit the lowest impact energy, whereas the transverse orientation having the notch parallel to the whisker axis was found to exhibit the highest impact energy. A significant differnce was noted between the impact behavior of material containing needlelike whiskers and that containing bladelike whiskers. Only two of the six orientations studied exhibited complete fracture for the material containing needlelike whiskers. On the other had, most of the specimens containing bladelike whiskers exhibited complete fracture. It was postulated that the bladelike whiskers block transverse flow, thus reducing the amount of plastic deformation ahead of the crack tip. One of the more significant advantages of composite materials is the prospect of combining high strength with toughness. In general, toughness is associated with materials which exhibit considerable ductility and can deform plastically in the presence of a stress concentration. Very strong materials which resist plastic deformation generally exhibit low toughness. At first glance, then, it would appear as though strength and toughness are mutually incompatible so that useful engineering materials would have to be a compromise between the two. One approach to the problem of combining the high intrinsic strength of ceramics with the toughness of metals was to mix them together to form a cermet. Unfortunately, the toughness of cermets was found to be rather disappointing. Whisker reinforcement of metals, however, appears to be a more promising approach. It has been demonstrated that whisker-reinforced metals produced by unidirectional solidification exhibit enhanced strength due to the presence of high strength nonmetallic whiskers. The total strain capacity of these composites in the direction of fiber alignment is limited to that of the fibers, the matrix being unable to carry the load once the fibers have failed. A characteristic, then, of whisker composites is low ductility in the direction of whisker alignment, on the order of a few percent elongation. This low elongation, which is usually associated with brittle behavior, should not be taken as an indication of low toughness. Such a material can exhibit significant ductility in directions other than parallel to the fibers7 and can therefore possess significant intrinsic toughness. Toughness in a fiber-reinforced metal is derived from several mechanisms. The first is due to the toughness of the matrix itself. A continuous ductile metal matrix can act as an effective crack arrest medium by undergoing localized plastic deformation. Cracks initiated from the surface of the composite or from a brittle fiber failure must travel through the matrix before reaching another brittle phase particle. A second crack arrest mechanism peculiar to fiber composites is due to the fact that, as a crack travels through the matrix and approaches a fiber, the plastic deformation ahead of the crack tip will result in loading of the fiber. This causes the matrix shear strength in the plastic zone to be apparently higher, thus extracting more energy from the crack and diverting the crack at an angle to the original direction of propagation. A third crack arrest mechanism occurs in fiber composites which exhibit a weak bond between fiber and matrix. The idea was proposed by Cook and Gordons that if a crack propagating transversely in a fiber composite were made to turn and run along the fibers by decohesion of the fiber-matrix bond, then toughness would be imparted by the blunting of the crack tip and the creation of new surfaces. The last mechanism, interfacial decohesion, is commonly noted in naturally occurring fiber composites such as wood, bone, and bamboo, and has been observed in man-made composites such as glass fiber-reinforced resins,g silica fiber-reinforced aluminum," laminated steel," and tungsten and silica fiber-reinforced electroplated copper.'' The first mechanism, crack arrest by plastic deformation in the matrix, has been noted in tungsten wire reinforced cast copper." The purpose of this investigation was to quantitatively assess the toughness of a whisker-reinforced metal as a function of orientation. Previous investigation considered only cracks propagating nominally perpendicular to the reinforcement. In this investigation, crack propagation in three mutually perpendicular directions as well as three intermediate orientations was investigated. The system chosen for study was the unidirectionally solidified A1-A13Ni eu-tectic alloy which has a microstructure consisting of 10 pct by volume of A13Ni whiskers in a matrix of aluminum This material exhibits two different kinds of whisker morphology, depending upon the rate at which it is solidified.' At low rates of solidification (less than 2 cm per hr) the whiskers are bladelike, whereas at higher rates of solidification they are
Jan 1, 1969
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Institute of Metals Division - High-Temperature Creep of TantalumBy W. V. Green
Creep of tantalum was measured at temperatures from 0.6 to 0.89 of the absolute melting temperature. The creep curves include first, second, and third stages. Steady-state creep rate depends on the fourth power of stress. The activation energy for creep throughout this temperature range is approximately 114 kcal per mole, measured by the aT technique. Subgrain formation occurs as a result of creep strain, and pile-up dislocation arrays are observed in etch-pit patterns. BECAUSE of its high melting point-which is exceeded only by those of rhenium and tungsten—and its high room-temperature ductility compared to most of the other high-melting-point metals, tantalum will undoubtedly be utilized in an increasing number of high-temperature applications. Alloying studies directed toward increased high-temperature strength must use data on tantalum itself as a base line in order to evaluate the effectiveness of the alloying additions. However, to date, no systematic study of creep of tantalum at temperatures above one-half of its melting point has been reported in the literature. Conway, Salyards, McCullough, and Flagella1 have measured linear creep rate of tantalum sheet as a function of stress, but at only one temperature, 2600°C. This paper describes a relatively thorough study of the high-temperature creep of tantalum. METHOD Material Tested. The commercially supplied, l/2-innch-diameter tantalum rod used for this work was electron-beam-melted, cold-forged, rolled, swaged, cleaned chemically, and vacuum-annealed for 1 hr at 1000°C, all by its manufacturer. The vendor's analysis included 60 to 170 ppm C, 3.4 to 4.2 ppm H, 60 to 80 ppm 0, 15 ppm N, and a hardness ranging from 66 to 81 Bhn and averaging 76 Bhn. Creep eimens Used. Two creep-tested specimens are shown in Fig. 1. The 1/4 in.-diameter gage section was 3/4 to 1 in. long, and terminated either at shoulders 5 mils high or at 20-mil-diameter tantalum wires spot-welded to the circumference of the gage section. Both kinds of shoulders served equally well as fiducial marks for optical strain measurements. The spot welding did not alter the creep behavior in any detectable way; the 5-mil- high sharp shoulders did not result in any detectable localized effect on the strain. Before testing, each tensile bar was first mechanically polished -id then electrochemically polished according to the method referred to by Forgeng2 as the "Thompson Ramo Woolridge" method, which was suitable for tantalum after small adjustments of technique were made. Two tensile bars tested at low stresses had 1/8-in.-diameter gage sections and utilized only the weight of the bottom grip for the applied load. Although these diameters were smaller than were desired for other reasons, applied loads were known with high precision in the tests in which they were used. Testing Procedure. Two different constant-load creep-testing machines were employed, one of which has been described by Smith, Olson, and Brown.3 In both, the tensile bar is held vertically on the axis of a cylindrical tungsten tube or screen heater by threaded tungsten grips. The tensile bars and associated grips are heated by radiation from the incandescent heaters, which are heated by their own electrical resistance. Both testing machines use pins to hold the bottom grips in place. The load is applied to a tensile bar through hanging weights, a constant force-multiplication lever, a pull rod sealed to the chamber lid, and a top grip threaded to the pull rod at one end and to the tensile bar at the other. In one machine, the vacuum seal is a bellows with a low spring constant; in the other, the seal involves a rotating "0 ring". With the latter, rotation is converted to translation with a crank shaft, so that elongation of the tensile bar is accommodated with no change of tensile load. The incandescent tensile bar is viewed by an external optical system through slots in the radiation shields and heater, and an enlarged image is projected on a ground-glass screen. Gage-length measurements are made on this image with cathetometers on traveling microscopes. With regard to creep-test results, the two machines were identical. Thorium oxide coatings were applied to the threaded ends of the tensile bars, to prevent diffusion welding of the tensile bars to the grips during testing. Specimen temperatures were measured with an L. & N. optical pyrometer which had been calibrated against a standard carbon arc, and were corrected fir window absorption by calculation from the measured spectral transmittance of the quartz observation windows. Longitudinal temperature gradients in the tensile-bar gage length and temperature drifts during testing were detectable but small, and were estimated to be 10°C or less. Accuracy of temperature measurement was confirmed by comparing the temperature measured on the surface of a special
Jan 1, 1965
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Producing-Equipment, Methods and Materials - Sand Movement in Horizontal FracturesBy H. A. Wahl, J. M. Campbell
This study extends our information on solid-liquid slurries to the flow of sand in horizontal fractures. Inasmuch as this is basically an unsteady-state process, a comprehensive photographic study was undertaken in a 10-ft windowed cell to determine if the basic flow regimes described for steady-state flow in pipes applied to the subject process. Since the number of potential variables far exceeds the capacity of a single study, emphasis has been placed on the effects of sand concentration, oil viscosity and oil flow rate. The extensive photographic evidence obtained has proven very valuable in gaining an insight into the basic flow mechanisms. Being able to follow visually the flow characteristics that accompany the quantitative data is valuable in the application of the results. Although the use of dimensionless parameters was carefully investigated. it was found that the data obtained could be more easily, and as accurately, correlated by judicious use of the dimensional variables investigated. However, a study into the feasibility of scaling slurry flow was made in the event this technique is justified in future investigations. The data presented show that the pressure behavior observed in solids transport in pipes basically applies to slurry flow in horizontal fractures. The roles of the parameters are altered but a basic equivalence exists. The most significant correlating parameter was the oil viscosity (µo) and the bulk velocity of the slurry (vn), expressed as ''µv" product. The most significant correlation expresses the rate of advance of the sand as a function of the variables investigated. There are many practical ramifications of this phase of the investigation that should aid in better treatment design. Evaluation of sand advance rates provides a means of estimating sand placement efficiencies during a treatment and the resulting sand distribution in the fracture. The results show that sand placement efficiencies are low under typical treatment conditions. A brief description of the effects of overflushing is also included. INTRODUCTION The flow of sand-oil slurries in fractures is an area in which little basic knowledge is available. This stems to some degree from the fact that it is impossible to duplicate fractures at the surface. They occur in various shapes and sizes with an infinite combination of irregularities. Unfortunately, we can never "see" these fractures except in cores and by indirect means of measurement. In spite of this inherent difficulty, it is desirable to develop some basic concepts that will provide a better understanding of the sand transport mechanism. An insight into the problem is provided by investigations of fluid flow in rectangular conduits. Several studies on the flow of liquids in non-circular conduits1,13 show that a Reynolds number-Fanning friction factor relationship can be written if the hydraulic diameter is substituted for the regular diameter in a circular pipe. This hydraulic, or equivalent, diameter is taken as four times the cross-sectional area occupied by the flowing fluid divided by the wetted perimeter. Eq. 1 expresses an extension of this same work when applied to infinite parallel planes b distance apart.' Eq. 1 is a theoretical equation expressing the friction factor as a function of the Reynolds number for laminar single-phase fluid flow. This expression has been verified experimentally. The equivalent expression for a smooth circular conduit differs only in that the value of the constant is 16 instead of 24. Numerous studies have related friction losses to Reynolds number in both circular and non-circular conduits. These results are widely used and are not reviewed here. Huitt' investigated the effect of surface roughness on fluid flow in simulated fractures. He concluded that fluid flow in fractures may be treated similarly to fluid flow in circular conduits. This work, together with that of Nikuradse,' shows that surface roughness has no appreciative effect upon the resistance to flow in the viscous flow region. In the region of turbulent flow, surface roughness is a prominent factor. Hydraulic conveyance literature is another important source of information. Durand3 has attempted to organize systematically the variables involved in hydraulic-solid transport in pipes. He has classified the modes of flow into three types according to the size of the particles in the mixture— homogeneous mixtures, intermediary mixtures and heterogeneous mixtures. With the usual concentrations and flow rates used in hydraulic transportation, particles with diameters of less than 20 or 30 microns form eszentially homogeneous mixtures with water. The data show, however, that even small materials will tend to settle out under laminar flow conditions. Mixtures containing solids over 50 microns in diameter do not achieve total homogeneity even under turbulent flow conditions. Particles from 50 microns to 0.2 mm in diameter may be transported in fully suspended flow at normal transport velocities although the concentration in the vertical plane is not uniform. Above 2 mm in diameter solid materials are transported along the bottom of the conduit at a velocity substantially less than that of the liquid itself. Between 0.2 and 2 mm in diameter, the particles tend to be in a transition zone between heterogeneous suspended flow and deposit flow at normal hydraulic transport velocities. The sand sizes used in fracturing usually fall in this size range. It is interesting to note that the grain size range designated by Durand for this transition zone corresponds closely to the transition zone between
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Concerning CoalCOAL is perennially -a subject of major interest at. Pittsburgh, but during the week of Nov. 19 to 24 it was especially to the fore because nearly two thousand persons gathered to take part in the second of the international conferences organized by President Baker of the Carnegie Institute. From the opening session on Monday morning when those attending were welcomed by President Baker and T. P. Gaylord, president of the Chamber of Commerce of Pittsburgh, until the party returned from the Clairton coke ovens on Saturday. afternoon, there was something going on all the time, and usually three sessions were in progress at once.
Jan 1, 1928
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Iron and Steel Division - Desulphurization of Pig Iron with Pulverized LimeBy Ottar Dragge, C. Danielsson, Bo Kalling
THE desulphurizing of pig iron has been accomplished with a number of different additions. The oldest and still most commonly used agent is soda, the extensive use of which commenced about 1925, when it was used principally for cupola furnace iron. More recent experience' seems to show that better results can be obtained with sodium hydroxide. The well-known desulphurizing properties of lime have also been exploited in different technical processes. Another material with even more powerful effect is calcium carbide.' The desulphurizing ability of manganese, when added to the ladle in sufficient quantity, should also be mentioned in this connection. During recent years increasing attention has been paid to the desulphurizing properties of metallic magnesium." An addition of a suitable alloy of magnesium is now in use purely for the purpose of sulphur elimination. Of the desulphurizing agents mentioned, lime is by far the cheapest, provided that the reaction can be brought about rapidly and completely. Therefore, a method that makes full use of the desulphurizing ability of lime may be able to compete with other processes. A method developed at the Dom-narfvet Iron and Steel Works (Sweden) will be described, which enables pig iron to be rapidly desulphurized to very low sulphur contents by using a burnt lime powder. as the desulphurizing agent. Lime in Older Processes In cases where lime has been used for the desul-phurization of pig iron, it has generally not been used alone, but mixed with other substances such as fluorspar, to obtain the formation of a molten slag during the process. This method has been tried by Tigerschiold,' who treated the iron with a lime-fluorspar mixture, the stirring of the iron being brought about inductively with low frequency alternating current. Very good results were obtained. A process of this type has also been suggested by R. P. Heuer, U. S. A. The principles of this method, which has been tested in Great Britain by Newell. Lanener. and Parsons." re that a mixture of lime and fluoispar is added to the hot metal in the ladle, while a powerful stream of nitrogen gas is blown into the bath to produce the required intermixing. The results of the tests were unsatisfactory, however. A similar process has been developed at The Steel Co. of Canada, according to a statement by H. M. Griffith.' Here the tests were carried out in a carbon-lined ladle provided with carbon tuyeres in the side wall for blowing nitrogen into the bath. The addition consisted of about 20 lb of a mixture of burnt lime and fluorspar per ton of pig iron. Good results appear to have been achieved. The sulphur content of the pig iron is stated to have been reduced from 0.025 to 0.050 pct down to 0.006 pct. Various methods of desulphurizing pig iron have been tried using lime powder without fluxing material for fusing. Eichholz and Behrendt7 have experimented with blowing a powdered limeicoke mixture with air into the ladle. Their results were, however, not conclusive and the experiments do not appear to have been continued. Similar experiments have been carried out at Domnarfvet, using nitrogen instead of air in order to avoid oxidation. But these attempts were not particularly successful. It appears to be difficult to achieve the required agitation by this means. The strong cooling effect of the gas on the iron is also a serious drawback. A method in many respects similar to that tried at Domnarfvet was tried by Eulenberg and Krus at the end of the 1930's. Here again desulphurization was carried out with lime alone, brought into contact with the molten iron in a rotary furnace. The temperature was kept at the required level, 1400" to 1500°C, by the introduction of a pulverized coal burner in one end of the furnace. The speed of rotating was not given. A paper by Bading and Krus states that, in one of the first experiments, the sulphur content in 56 tons of pig iron was brought down from 0.186 to 0.035 pct in 117 min, but that a considerable shortening of the time would be possible. According to later reports by Eichholz and Behrendt,' it should be possible by this process to achieve a desulphurization speed of 0.35 pct S per hr for a consumption of 6 to 10 pct limestone and 2 to 3 pct coke, as fuel exclusively. The final sulphur content is, however, not stated. Domnarfvet Method After a number of different procedures had been investigated, the tests at Domnarfvet were directed to desulphurization with lime in a rotary furnace. Before going into the practical details of the method, the theoretical aspects will be discussed briefly. If the pig iron does not contain alloying elements other than carbon, the reaction can be expressed most simply by the usual equation: FeS + CaO + C = Fe + CaS + CO [I] 4H,. ~ 34,000 cal That this reaction can be carried through to a very complete desulphurization of pig iron has been shown by OelsenD in a discussion in connection with the Eulenberg and Krus' method. He mentions two laboratory tests, in one of which the sulphur content in the pig iron at 1400°C was reduced from 0.540 to 0.006 pct after treating with 3.35 pct lime. The pig iron had a low manganese content, but other analysis is th. given. Mention also should be made of the recently published investigations by Fischer and Cohnen'" dealing with the influence of the carbon content of the iron on desulphurization with lime, although in this case fluorspar was added also. The tests show that efficient desulphurization is possible with lime in the steel bath, provided that the carbon content is sufficiently high. The temperature employed in these tests was considerably higher (1620") than that normal for treatment of pig iron. The author concludes that the product S% X C% - 0.011 at the temperature in question.
Jan 1, 1952
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Coal - Underground Anemometry - DiscussionBy Cloyd M. Smith
B. F. TiLLson*— The manifold difficulties of accurate anemometry in irregular sections of mine passageways, the irregular distributions of velocities in cross sections of the same, and the disturbing influence of the observer upon the air flow, all indicate an undesirable inaccuracy of results obtainable by any standardized method of traversing the section by an anemometer. It seems obvious that another, and simpler, method should be used to determine the volume of air flow in mine passages, namely: 1. At appropriate locations cement or calked framework rings should be installed permanently to equalize the irregularities of sectional contour and provide a place and means of attachment for a temporary cloth brattice which bears a rigid orifice. 2. The measurement of the velocity of air flow through the orifice may then be by anemometer or, preferably, by Pitot tube measurements of the differential pressures on both sides of the orifice in accordance with the standard practices available in engineering 1iterature. † The constants may be determined for various measuring positions in relation to the resulting "vena contracta." 3. The position of the person who makes the measurements is behind the brattice out of the air stream. The Pitot tube does not offer as disturbing an obstruction as the anemometer. A recording gauge may be employed to integrate fluctuations in air flow through that portion of the mine. No traverses are required because the reading may be at a single central point. An anemometer can be used with an orifice flow. The orifice will increase the air velocity at the measuring point, with correspondingly more accurate measurements where the normal air velocity through the passageway is low. Portable brattices might be devised with the cushioning rims which would seal against irregular rock surfaces where permanent rings were not available or feasible. The development by the Ventilation Committee of standard procedures and devices for the orifice measurement of the flow of mine ventilating air might be a desirable project for this coming year. C. M. Smith (author's reply)—Thank you for your discussion of my paper on underground anemometry. Your suggested method of measuring underground air flow is a novel one which might be applicable in some situations. It should be tested along with other suggested methods in any investigation of this subject. G. E. McElroy*—In spite of the adverse publicity that vane-anemometer methods of air measurement have had in the past and that contributed by the present paper, I endorse Mr. Erickovic's statement that anemometer traversing "has proved to be widely applicable, expeditious and simple" and add that available methods are accurate enough for the purposes for which they may be used. The fact that the great majority of minor mine officials assess relative changes in rates of air flow by comparison of crude vane-anemometer measurements, known to average 20 to 30 pct high, has no important bearing on this subject, because state inspection standards were based originally on such methods of air measurement. Federal inspection standards are based on actual rates of flow as determined by traversing, and interest in traversing methods is rapidly increasing. In considering traversing methods, three aspects are of major importance: (1) the absolute accuracy of calibrations; (2) the degree of interference with normal flow conditions introduced by traversing methods designed for accurate measurement by shaft-mounted instruments; and (3) the proper "method" factor to use for approximate measurements by hand-held instruments. With respect to absolute accuracy of calibrations, we have always placed reliance on calibrations made by the National Bureau of Standards, with which manufacturers' calibrations have usually agreed very closely. It is therefore particularly disturbing to find7 that calibrations made previous to June 1947 are presumably about 5 pct in error because of excessive registry caused by the thin flat plates on which anemometers were mounted for calibration. Velocities corrected for calibration have therefore averaged about 5 pct low in all probability. In this connection, it is interesting to note that an anemometer calibrated against Pitot-tube measurement by a single-point method in the Bureau of Mines experimental coal nine in 1923 indicated this same difference of about 5 pct and that the same instrument calibrated by a traversing method in a metal mine some months later indicated a difference in the same direction of about 4 pct. These results are reported by the Bureau of Mines.8 Regarding the degree of interference, or changes in velocity distribution, caused by the position of the observer's body in traversing operations, misconceptions seem to be especially prevalent, resulting in increasing advocacy of methods, such as the "clear section" method outlined in this paper, that cause just the type of interferences that they are designed to avoid. The degree of interference for any method may be gauged easily by a few experiments with a velocity-pressure gauge connected to a Pitot tube or with an indicating velocity meter such as the Velometer. In an experiment cited by McElroy and Richardson,# a decrease of 5 pct was noted at ten widths upstream from a 6-in. plank, whereas an observer's body at about the maximum practical distance of 6 ft downstream from the instrument is only about four widths away. In the Bureau of Standards paper previously mentioned, it is recommended that supports used in calibrations be at least 16 widths downstream. In practice, therefore, a downstream position of the observer is ruled out as far as accurate measurement is concerned. Operation of the anemometer by rigid shaft support from a point outside the section is seldom practicable; however, accurate results can be obtained, with the anemometer rigidly attached to a short shaft and held at arm's length, by an observer advancing across the traversed section while he faces the opposite wall and stands sideways to the current, provided that he keeps the instrument at least 3 ft away from his body at all times and traverses the entire section with it. If the traverse can be started with the observer in a side recess, the entire section can be covered in one operation. Normally, it would be covered in two half-sections. The presence of the observer's body does not, as is commonly supposed, increase the average velocity throughout the remaining part of the section. Rather, the velocities 1 to 2 ft on either side of his body are increased, but the distribution of velocities throughout the rest of the cross section remains normal, and a traverse made as stated gives a true average velocity for normal-flow conditions. Regarding the proper "method" factor for accounting for interference in the approximate methods of traversing with hand-held instruments, here again confusion prevails, for which the writer must assume some of the blame. Comparison of consecutive traverses made by shaft-held and hand-held 4-in. anemometers in field work after the tests reported by McElroy and Richardson' gave method factors
Jan 1, 1950
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Part III – March 1968 - Papers - A Survey of Radiative and Nonradiative Recombination Mechanisms in the III-V Compound SemiconductorsBy P. J. Dean
This Paper contains a comprehensive survey of the known electron-hole radiative recombination mechanisms in the family of III-V compounds. Because of space limitations, the luminescence properties of each III- V compound are not reviewed separately and exhaustively. Instead, the different known types of recombination processes are discussed in turn and exemplified with reference to the III- V compound in which they were first recognized, or are best understood. Electron-hole recombinations usually occur predominantly at impurities or lattice defects either introduced de1iberately or inadvertently present, but radiative intrinsic interband electron-hole recombinations, which occur in perfect crystals, have been observed. Recombination processes which involve the participation of impurities or lattice defects ("extrinsic" recombinations) considered include transitions in which a) free carriers recombine with carriers trapped at impurities ("free to bound" transitions) , b) electrons bound at donor impurities recombine with holes trapped at acceptor impurities ("donor-acceptor pair" recombinations), C) excitons bound to charged or neutral donor or acceptor impurities recombine radiatively (both "resonance" and "two-electron" "bound exci-ton" transitions have been observed), d) excitons bound to neutral donor or acceptor impurities recombine non-radiatively (an example of an "Auger" recombination), and e) excitons bound to impurities with the same number of valence electrons as the host atom which they replace ("isoelectronic " traps) recombine radiatively. In addition, Auger recombination processes involving one or more free carriers have been observed. These extrinsic processes all involve impurities which are present as point defects. Some apparently well-authenticated examples of the recombination of excitons bound to complex impurity-lattice defect centers including nearest-neighbor donor-acceptor pairs are also discussed. Identificalions of the transitions involved in stimulated emission from the direct gap III-V compounds are briefly reviewed. Although the examples of these recombination mechanisms are selected from the III-IV compounds ia this review, these processes have quite general relevance in semiconducting crystalline solids; irrdeed most of them have also been identified in the 11- VI compounds and elernental semzconductors. THE development of crystal growth and purification techniques in recent years and concurrent advances in the understanding of physical processes in solids has accelerated the development of a wide variety of solid-state electronic devices of proven utility. These de- vices are generally used for switching or amplifying operations in electrical circuits. Most solid-state circuit elements are very photosensitive. This photo-sensitivity is generally undesirable and the single-crystal chip forming the active portion of the solid-state device is mounted in an opaque container. The photosensitivity is made use of in phototransis-tors and photodiodes, which are among the most sensitive detectors of electromagnetic radiation particularly in the near infrared.' In these devices, light is converted into electrical power. The solid-state lamp utilizes the inverse effect, namely the conversion of electrical power into light. There is an increasing tendency to use single-crystal diodes rather than the earlier electroluminescent cells in which the active material is present as a powder embedded in a suitable dielectric.' The radiation is emitted at a rate far in excess of the thermal equilibrium rate for the frequencies and temperatures involved; i.e., luminescence occurs. The development of practically efficient solid-state lamps is at an early stage compared with solid- state circuit elements or even photodetectors. Considerable progress has been made in recent years, however.3 The present review is devoted to a survey of the radiative recombination processes in the semiconducting compound crystalline solids formed from elements in groups I11 and V in the periodic table. These materials exhibit the full range of known recombination processes in solids. In fact many of these processes were discovered in 111-V semiconductors. Nonradiative recombination processes, which control the lutninescence efficiency, are also discussed. Luminescence is efficiently excited in semiconductors through processes which produce large excess concentrations of free electrons and holes in the energy bands of the crystal. Transitions induced by lattice defects or impurities usually predominate in the recombination process. By contrast, luminescence in the conventional fluorescent lamp is excited by optical absorption at the luminescent impurity center itself (the activator) and/or at a second type of impurity center (the sensitizer). This latter type of photoluminescence process, occurring in doped ionic crystals with wide band gaps, is outside the scope of this review.4 I) ENERGY BAND DESCRIPTION OF ELECTRON STATES IN CRYSTALS The energy band description of the energy states available to an electron in a crystal forms the basis of our understanding of the empirical division of crystalline solids into metals, semiconductors, and insulators in accordance with their electrical and optical properties.' Nonmetallic crystals have a finite energy gap between the highest energy band which is
Jan 1, 1969
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Part X – October 1968 - Papers - The Sb-TI-Te System: Phase Relations and Transport Properties in the Tellurium-Rich RegionBy J. V. Gluck, Ping-Wang Chiang
The tellurium-rich region of the Sb-TI-Te ternary system was investigated by means of DTA, metallo-graphic, X-ray, and electron beam microprobe techniques on the sections Sb2Te3-T12Te3, SbTlTe2-Te, SbT1Te2-Sb2Te3, and SbTlTe2-T12Te3. The phase behavior of this region is summarized in terms of four ternary invariant reactions and a schematic reaction diagram is suggested. Isopleths for the sections SbT1Te2-Sb2Te3, Sb2Te,-T12Te3, and SbTlTe2-Te were constructed, and a schematic diagram of the projections of the liquidus lines and invariant planes is presented. No evidence was found to support the existence of the ternary compound "SbTlTe3", or pseudo-binary behavior of the section T12Te3-Sb2Te3, as reported by Borisova and Efremova. Electrical conductivity, Seebeck coefficient, and thermal conductivity measurements were made at room temperature on fully annealed samples. 1 HE phase relationships in chalcogenides are often complex and difficult to resolve, particularly since the approach to equilibrium is a rather slow process. For example, the phase diagram of the T1-Te binary system was in doubt until clarified by Rabenau et al.,1 the phase fields at compositions near Bi2Te3 in the Bi-Te binary system have only recently been satisfactorily elucidated by Glatz,2 and there may still be some question as to the extent of the Sb2Te3 field in the Sb-Te system.3-5 In ternary systems, the existence of the compound "AgFeTe2" was the subject of a number of conflicting reports6-8 and the stoichiometry of the composition "AgSbTe2" was in doubt for a period of time.9 Recently, questions have arisen regarding the existence of certain compounds in the ternary systems Bi-Tl-Te10-14 and Sb-Tl-Te.15 The impetus for studies of these latter systems stemmed from the report of Borisova et a1.10 of a congruently melting ternary compound, "BiTlTe3", which apparently had extremely favorable thermoelectric properties for room-temperature cooling applications. Attempts by other investigators to produce the compound or confirm the transport properties proved to be unsuccessful.12-14 Recently, Chiang and Gluck14 reported studies of the phase relations in the tellurium-rich region of the Bi-T1-Te system which indicated that the section T12Te3-Bi2Te3 was not pseudobinary as suggested by Borisova et a1.10 The contention of Spitzer and sykes12 was supported that the composition "BiT1Te3" was multiphase, with the primary constituent actually being BiTlTe2, a compound whose existence has been well demonstrated.16,17 The investigation reported in the present paper was prompted by a later report of Borisova and Efremova15 on a similar study of the section T12Te3-Sb2Te3 from the Sb-T1-Te system. They also claimed this section to be pseudobinary, and that a ternary compound "SbTlTe," was formed peritectically. Some "preliminary" crystallographic data were given for the compound and thermoelectric transport properties were presented. In view of the questions concerning the behavior of the Bi-T1-Te system and the existence of the compound "BiT1Te3" it was suspected that the Sb-T1-Te system might behave in a similar fashion, particularly in light of the known existence of a compound SbT1Te2, iso-structural with BiT1Te2.17 Consequently, an investigation was undertaken to clarify the phase relationships in the tellurium-rich region of the Sb-T1-Te system. It is the purpose of this paper to present the results of this study, including a representation of the phase relations, isopleths for various composition sections, and the determination of some phase compositions and transport properties. EXPERIMENTAL PROCEDURES Commercially available high-purity (99.999+ pct) elements, purchased from the American Smelting and Refining Co., were used for the sample preparation. All samples were made from thoroughly mixed powders of previously prepared master alloys: SbTlTe2, Te, Sb2Te3, and T12Te3. Stoichiometric quantities of the constituents for each 10-g sample were weighed into a specially cleaned fused silica tube and sealed under a vacuum of better than 5 x 10-5 torr. The sealed constituents were fused and reacted at 650° to 750°C for at least 4 hr under continuous agitation in a "rocking" furnace, and the resulting product was air-cooled. The tube was opened and the sample was ground to a powder. A portion of the powder was rebottled in a DTA tube under vacuum, and the rest of the material was similarly resealed in a separate tube, re-fused in the rocking furnace, and again cooled to make the ingots for electrical and microstructural studies. All samples were subjected to further heat treatments as discussed in the section on experimental results. Each DTA tube was made of 7-mm-OD fused silica tubing with a concentric 2-mm-ID depression about 4 mm long formed in the bottom to accommodate a thermocouple. The size of a DTA sample was 0.5 to 1.0 g. An Aminco Thermoanalyzer whose accuracy was within 2°C18 was used for the DTA measurements. The metallographic samples were prepared by conventional techniques. A solution of FeCL dissolved in a methanol-HC1 mixture was found to be the most satisfactory etchant. Electron beam microprobe scanning and point-count examinations were made on polished and unetched samples using an ARL Electron Microprobe at an electron beam voltage of 20 kv. The detectors were set to receive characteristic La1 radiation. Calibration standards of the pure elements were incorporated in each sample mount; quantitative point counts were calibrated by a method similar to Ziebold
Jan 1, 1969
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A Review of Subsidence Experiences in the Southern Coalfield New South Wales, AustraliaBy William A. Kapp
INTRODUCTION Coal is being mined from beneath residential areas, structures, bodies of water and other surface features in the coalfields to the north, south and west of Sydney. The particular problems faced by mine operators in these areas vary considerably due to differences in the overlying strata, the variation in the depths of cover and also depend on the number of seams being mined. Detailed subsidence work first commenced in the Southern Coalfield in 1965 and is now being carried out over areas of extraction at roost collieries. The analysis of the results of the early investigations and of the work which continues in other areas has shown that there is a consistent relationship between subsidence and mine geometry and has led to a reliable empirical method for the prediction of subsidence. In addition, particular aspects of each of the studies in the Southern Coalfield results in a clearer understanding of strata movements and of the resulting subsidence. The features of a subsidence trough apply generally to all areas but the magnitudes of specific features vary according to the stratigraphy of the particular coalfield. The aim of the subsidence work is to quantify the effects of subsidence for a range of mining geometries and mining conditions to enable the maximum safe recovery of coal from beneath surface features. The importance of local subsidence investigations is becoming more evident to mine operators and to authorities or organisations with surface interests. The subsidence work also provides important information on the stabilities of pillars of coal which remain unmined between panels of extracted coal. These pillars are not extracted either because of poor mining or geological conditions, or because pillar extraction is not part of the particular mining operation. Subsidence studies over these coal pillars clearly establish whether the pillars have remained stable or have failed to support the overlying strata. With subsidence studies continuing over several years, it is possible to assess the stabilities of these pillars on a long term basis. BACKGROUND TO THE STUDY OF SUBSIDENCE Geographical setting Most of the black coal production in Australia comes from the Sydney Basin. The coal seams extend for approximately 350 km along the coast of New South Wales and inland for distances up to 150 km. The City of Sydney is located near the centre of the coastal extent of the Basin where coal has been mined at a depth of 900 m. The Sydney Basin is part of the Main Coal Province of NSW and is divided into several coal- fields. The Southern Coalfield to the south of Sydney contained 15 operating mines and produced 12.7 million tonnes of raw coal during the 12 months to June 1981. The collieries discussed later are shown in Fig. 1. The prominent topographical feature of the area is the Illawarra Escarpment which rises to 400 m above sea level, or 300 m above the coastal strip along the South Pacific Ocean. The escarpment is mainly sand- stone and the weathering of the cliff line has resulted in a covering of talus material at its base. Several collieries are located near the seams which outcrop along the escarpment. The city of Wollongong is located in a scenically attractive area on the coastal plain. The suburbs of Wollongong extend north along the coastline, south to beyond Lake Illawarra and west to the lower slopes of the escarpment. The Illawarra Escarpment forms the eastern boundary of the Woronora Plateau. On a regional scale the surface dips gently to the west and thus forms a watershed for the rivers, most of which flow in a general north westerly direction, sometimes forming steep gorges in the sandstone. These rivers join the Nepean and Hawkesbury River system and flow into the Pacific Ocean north of Sydney. Seven dam have been constructed over the Southern Coalfield (Fig. 1) and with one large dam further to the west, their stored waters provide the needs of the Cities of Sydney and Wollongong and the surrounding districts. A large part of the area affected by mining is the undeveloped bushland of the associated catchment areas. In general no special precautions have been required with respect to subsidence with the exception of the dam structures and stored waters. With the increase in coal mining activities and the expanding residential development south of the City of Campbelltown in the outer Sydney Metropolitan area, subsidence is becoming an increasingly important area of research. Structures which have been affected or considered are townships and extensive residential areas, buildings of historical importance, major tollways, and a high pressure natural gas pipeline. The subsidence effects of mining beneath natural features within national parks is coming under study as mining approaches these areas. Geological setting The coal seams of the Southern Coalfield lie within the Illawarra Coal Measures. They contain high rank coking coal used in the local steel industry and for export. The Bulli Seam is mined extensively through- out the Southern Coalfield with the lower Wongawilli Seam being second in importance with regard to coal production. The top of the Bulli Seam is taken to be the marker horizon between the Permian Coal Measures
Jan 1, 1982
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Mining - Manufacture of Tungsten Carbide Tipped Drill SteelBy T. A. O’Hara
SINCE May 1948, when tungsten carbide bits were introduced at the Flin Flon mine, they have been popular with the miners because of their fast drilling speed and low gage loss. The high cost of commercial carbide bits and tipped drill steel, however, prevented their use except for the hardest rock. In an effort to extend the use of tungsten carbide on a basis economically competitive with detachable steel bits, experimental work was begun in 1950 to test the feasibility of making tungsten carbide tipped drill steel in the mine drill steel shop. This work showed that tipped drill steel could be made locally at less than half the cost of the commercial product. The performance of the local tipped drill steel was comparable to that obtained with commercial carbide bits and tipped drill steel and the cost per foot drilled was much lower. Local tipped drill steel was adopted for all mine drilling in November 1951. Since then drilling costs per foot have been sharply reduced and footage drilled per manshift has increased markedly. Experience at Flin Flon has shown that production of satisfactory carbide tipped drill steel is not difficult and that highly skilled labor and costly equipment are not required. As long as wise selection of brazing materials is made and certain simple precautions are rigidly maintained, there is no reason why small mines with relatively unskilled labor cannot produce a satisfactory product. The following description outlines the technique used at Flin Flon for making carbide tipped drill steel and discusses characteristics of the brazing process that make special precautions necessary. Drill steel is forged to four-wing shape in a conventional steel sharpening forge. Standard steel dies are modified to minimize forging cracks around the central waterhole and to forge a blunt bithead on the steel. The steel is preheated to 1500°F and held at this temperature for at least 2 min. When the temperature has equalized throughout the steel section, the drill steel is transferred to the forging furnace and heated rapidly with a reducing flame up to 2000°F. This two-stage method of heating minimizes the grain growth and decarburization of the steel while ensuring that the steel temperature does not vary greatly throughout the forging zone. After forging the steel is allowed to cool in air to about 1600°F before being annealed in a bath of vermiculite. Despite the high hardenability of the 3 pct Ni-Cr-Mo drill steel used, this simple treatment anneals the drill steel sufficiently for milling. The forged and annealed drill steel is slotted on a plain horizontal milling machine that is equipped with a quick opening chuck and a slot depth stop. The full depth of the slot is milled in a single pass of the 3-in. milling cutter which is fed at 33/4 in. per min across the crown of each bit wing. The slots are cut to a width of 0.342 to 0.344 in. Maintenance of this slot width is necessary to ensure that the optimum brazing clearance of 0.002 in. will result after assembling of shims and carbide in the slot. Prior to March 1953, when the milling machine was installed, drill steel was slotted on a small manually fed ¾ hp milling attachment mounted on the bed of a lathe. Over 16,000 drill steels were slotted on this unit, and in view of its small size and low cost it gave excellent service. Brazing of Tipped Steel Drill steel that has been milled and cleaned in carbon tetrachloride is mounted in a rotating cradle holding six drill steels, the length of which may be from 2 to 12 ft. The slots in the drill steel, the shims, and the tungsten carbide inserts are thoroughly fluxed with a fluoride flux and assembled as shown in Fig. 1. Fig. 2 shows the brazing equipment in use. As the ring burner is lowered over the bithead a spring valve opens the gas lines, and the gas mixture, preset to give a slightly reducing flame, is fed to the ring burner where it is lit from a pilot flame. The ring burner heats the drill steel over a zone about 1 to 2 in. below the bithead, which becomes heated by conduction through the steel. By this means the bithead is heated rapidly and evenly, and contamination of the brazing joint with soot from the flame is avoided. The bithead is heated to the melting temperature of the brazing alloy within 1 min. This rapid heating minimizes the disadvantage of a non-eutectic brazing alloy. The brazing alloy, a nickel-bearing quaternary alloy, is placed at the bottom of the slot below the carbide insert, as shown in Fig. 1. As the brazing alloy melts it is drawn by displacement by the carbide and by capillary action into all parts of the joint to displace liquid flux from metal surfaces. As soon as the brazing alloy melts, each insert in turn is wiped by being moved back and forth along the slot. This action assists wetting of the carbide by the brazing alloy and assists in displacing molten flux from the joint. After continuous heating for about 75 sec, when the bithead has reached a temperature of about 1500°F, the ring burner is raised and the gas supply is shut off automatically by the spring valve. As soon as heating is stopped a hand press is placed on the bithead and the inserts are squeezed down firmly. This action minimizes the clearance between the bottom of the insert and the slot. Correctly brazed steel should maintain a clearance at the bottom of the slot of 0.001 to 0.002 in. After six steels have been brazed they are removed from the cradle and allowed to cool in air. As soon as each drill steel is cool it is dressed on a grinding wheel to remove excess flux and braze and is ground to the gage appropriate to the length of the drill steel.
Jan 1, 1955