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By H. C. Chao, L. H. Van Vlack

Small MnS inclusions with known crystallographic orientations were placed inside powder compacts of low-carbon steel. After the metal was axially campressed with negligible end friction, the deformstions for the metal and the inclusions were compared. The MnS inclusions deformed more when the [100] direction was aligned with the compression axis than when the [111] direction was parallel to this axis. The deformations of the inclusions in the two principal radial directions were equal for each of the above orientations. Inclusions with [110] compression alignments did not deform with radial symmetry. The relative deformation of the inclusion and metal was closely dependent upon the relatiue hardness of the two phases. The relative deformation of the two phases was not sensitive to the rate of deformation. RECENT studies by the authors1.&apos; suggested that the plastic deformation of MnS in steel would probably be highly sensitive to the orientation of the inclusions and to the temperature of the metal. This paper reports an investigation of these factors upon MnS behavior within steel. Manganese sulfide (MnS) possesses an NaCl-type structure and typically has extensive (l10) {110} slip as a separate (noninclusion) crystal.&apos; A secondary slip system, ( l 10) { l l l}, has also been observed where the major slip system is restricted. In general, MnS inclusions must be rated as a highly deformable second phase.3 The amount of sulfide deformation varies, however, with several composition and processing factors. Some of these have been only partially assigned. For example, it is known that minor amounts (<0.01 pct) of silicon within free-machining steels will increase the amount of MnS deformation,4 but the mechanism of the added deformation can only be surmised at the present. Manganese sulfide and steel have sufficiently comparable deformation characteristics so that slip which is started in steel may be continued through the sulfide inclusions and back into the steel if the crystal orientations are favorable.5 A more detailed discussion of previous work on the plastic deformation of NaC1-type crystals and on the plastic deformation of inclusions within a metal is given in Chao&apos;s work.6 EXPERIMENTAL PROCEDURE The manganese sulfide which was used in this study was prepared by previously described methods.&apos; Single crystals of MnS, both as cleavage cubes and as spheres, were oriented within steel powder compacts so that the desired crystal directions were parallel to the direction of axial compression. A four-stage hydrostatic compaction procedure was used and involved the following steps. In the first stage part of the powder was placed in a metal die 1 in. in diameter with a thick (1 in. OD, 5/8 in. ID) rubber liner which had one end plugged. The steel powder was hand-rammed, making it as dense as possible before placing a carefully sized MnS crystal (either as a sphere or as a cube) near the center. The crystal was oriented with the chosen direction vertical; viz., [001], [011], or [111], with the aid of a X10 microscope. A pair of tungsten wire threads 0.020 in. in diameter was inserted along the side of this (&apos;core compact" to locate the desired plane after the compression tests. After the crystal was positioned in the center of the die, more powder was added and carefully rammed by hand. The die was then capped with a rubber plug of the same hardness and thickness as that of the liner. The whole assembly as shown in Fig. 1 was compacted by a ram load of 54,000 lb (about 70,000 psi). In the second stage a smaller, 3/4-in, rubber-lined die was used to give a stress of approximately 120,000 psi. The above process was repeated with the initial compact serving as a core for a larger compact. The final product after sintering was a cylinder 1 cm long and 1 cm in diameter, having a density of 7.54 g per cu cm. This was close to the theoretical density since the metal contained a non-metallic phase. There was no evidence of MnS deformation during the hydrostatic compaction or subsequent sintering. Elevated-temperature hardness data were obtained by procedures previously described.2 Compression tests for inclusion deformation utilized the cylinders which were described above. The critical problem in these tests was the lubri-

Jan 1, 1965

By Charles Catlett

THE rapid development of the Portland-cement industry implies that the country is being very carefully searched for material suitable for its manufacture. Such material can be found at a great many places ; but deposits thoroughly satisfactory in chemical composition, and at the same time meeting all the other requirements connected with the economic production and profitable marketing of the product, are exceedingly few, if I may judge from the investigations which I have had to make in a number of States. The raw mixture which by its clinking and grinding forms Portland cement contains approximately 75 per cent. of carbonate of lime. This is found in nature as limestone or marl. The natural rock commonly carries either more than the required percentage of carbonate of lime (in which case it has to be reduced by suitable admixture of clayey ingredients) or less-in which case purer lime carbonate has to be added. The controlling ingredient, therefore, is carbonate of lime, or limestone of the right composition. Among the most serious difficulties is that of finding limestones low enough in magnesia to meet the exacting requirements of certain specifications. All engineers recognize that there is a limit beyond which it is not safe to let the magnesia go; but within that limit there is considerable difference of opinion. Until that difference is finally settled, no one would be willing to invest the large sum of money necessary for a Portland-cement plant, if it were not certain that the usual requirements in this particular could be satisfied. The usual limit in well-established specifications is 5 per cent. of magnesium oxide in the finished cement, but many specifications limit the amount to 3 per cent. These figures

Jan 9, 1907

By R. A. Graham, R. W. Rohde

The effect of hydrostatic pressure upon the austenite start temperature of a commercial Fe-28.4 at. pct Ni-0.5 at. pct C alloy has been determined. For pressures to 20 kbar, the austenite start temperature decreased from its atmospheric pressure value of 380°C at the rate of about 4°C per kbar. These data are analyzed by two different thermodynamic approaches; first, considering the transformation as an isothermal process, and second, considering the transformation as an isentropic process. It was found that both these approaches fit the experimental data equally well. The effect of hydrostatic pressure upon the austenite start temperature is best described by considering the mechanical work done during the transformation as that work obtained by multiplying the applied pressure with the gross volume change of the transformation. It is widely recognized1 that strain has an important effect on the initiation of martensitic transformations.* For example, the martensite start tempera- *In this paper, use of the term martensitic transformation implies the reversal of martensite to austenite as wen as the formation of martensite from austenite. ture, M,, may be increased by plastic deformation. Similarly, plastic deformation is observed to lower the austenite start temperature, A,. The effect of uniaxial stress on the M, of iron-nickel alloys has been studied by Kulin, Cohen, and Averbach.2 They found that the martensite start temperature was significantly changed by stresses well within the elastic region. Moreover, the effect of tensile and compres-sive stresses differed. These effects were explained in terms of the interaction of the applied stress with both the dilational and shear components of the transformation strain. The magnitudes of the influence of uniaxial tension, compression and hydrostatic pressure on Ms were measured in 30 pct Ni 70 pct Fe by Pate1 and Cohen.3 Their thermodynamic calculations and similar calculations by Fisher and Turnbull4 predicted the experimental results when the transformation was assumed to occur isothermally at some fixed driving force. This driving force was assumed to be supplied by a combination of the chemical free energy difference between the austenitic and martensitic phases and the work performed during transformation by the applied stress. More recently, Russell and winchel15 reported the effect of rapidly applied shear stress on the reversal of martensite to austenite in iron-nickel-carbon alloys. They performed a thermodynamic analysis of this transformation based upon the assumption that the re- versal occurred adiabatically. They concluded that the applied shear stress did not significantly interact with the transformation strain and thus did not assist in inducing the reversal. Rather they concluded that the reversal was effected by localized strain heating which resulted from the gross local shear deformation of the experiment. In either the adiabatic or isothermal analysis it is necessary to compute the work performed by the interaction of the applied stress and the transformation strains. In the case of hydrostatic pressure this interaction has been treated by two different methods. In either case the applied pressure is assumed to remain constant during the transformation. In one treatment the applied pressure is assumed to interact directly with the dilatational strain associated with the formation of an individual martensite plate.3&apos;4 This local strain has been measured at atmospheric pressure in iron-nickel alloys by Machlin and Cohen.6 In the above treatment this local strain is assumed invariant with temperature and pressure changes. In the other treatment the applied pressure is assumed to interact with the gross volume change of the transformation.7,8 The usefulness of this latter treatment has been demonstrated by Kaufman, Leyenaar, and Harvey7 who calculated the effects of pressure upon the martensite and austenite start temperatures of Fe-10 at. pct Ni and Fe-25 at. pct Ni alloys. Excellent agreement was obtained between their calculations and their experimental data on an Fe-9.5 at. pct Ni alloy. However, this treatment suffers from the fact that the data required to calculate the volume change of the transformation (i.e., the initial specific volumes, the thermal expansion and compressibility data for both the austenitic and martensitic phases) is, in general, not available for any material except pure iron. Thus the calculations of Kaufman et al.7 were necessarily performed by assuming that the volume change of the martensitic transformation in the iron-nickel alloys was that same volume change occurring during the a-? transformation in pure iron. While this approximation may suffice for very dilute alloys it is likely to be inaccurate in high nickel alloys. We have performed measurements of the effect of hydrostatic pressure to 20 kbar on the A, temperature of an Fe-28.4 at. pct Ni-0.5 at. pct C alloy. The composition is similar to the alloy used by Pate1 and Cohen3 to determine the effect of pressure upon the M, temperature. The present measurements permit calculation of the interaction between the applied pressure and the transformation strain. Additionally, measurements have been made which allow precise determination of the gross volume change of the transformation. The data allow direct comparison between the alternate hypotheses of the interaction between the applied pressure and a dilatational transformation strain characterized by either the formation

Jan 1, 1970

By E. B. Branson

Introduction to Geology, by E. B. Branson, W. A. Tarr, and W. D. Keller, revised-by Carl C. Branson. McGraw-Hill, 1952. $5.50.-Dealing with physical and historical geology, the book has been revised from an earlier edition. An attempt has been made to eliminate unnecessary detail in discussing processes and history. Revisions bring technical and statistical data up-to-date, and follow suggestions by teachers who used earlier editions. The book carries an eye witness account of the severe earthquake in Assam, India, in 1950 and the story of Paricutin and other major examples of volcanism. Charts summarize chemical weathering, and the results of metamorphisms. The book also contains many new illustrations, including aerial photographs. A History of Phelps Dodge 1834-1950, by Robert Glass Cleland. Alfred A. Knopf, 1952. $4.00.-The book traces the growth of Phelps Dodge from the day Anson Greene Phelps opened a small saddle shop in Hartford, Conn., to the present day. As the country grew, so did Phelps Dodge. The company took part in large affairs from its very beginning. It bought and sold, exported and imported, built factories and railroads, and widened its scope of operations economically and geographically. Entrance of Phelps Dodge into copper mining and the gradual giving up of other interests in favor of the new venture is traced.

Jan 1, 1952

By L. W. Kemph, K. R. VanHorn

During the recent development of aluminum alloys for free-cutting screw-machine rod, it became desirable to know something of the solubility of lead and bismuth in liquid aluminum and in some aluminum alloys. The literature is not particularly helpful in supplying this information. These portions, therefore, of the constitutional relationships of aluminum-bismuth and aluminum-lead alloys were investigated by thermal analysis and by chemical analysis of samples taken from aluminum-rich melts in equilibrium with precipitated lead or bismuth. The solubility of lead and bismuth in some liquid aluminum-copper alloys was also investigated. Some consideration was also given to the solubility of these elements in solid aluminum. Among the earliest investigators of the aluminum-lead and alunlinum-bismuth systems was Wright,&apos; who reported that melts of aluminum and lead formed two layers indicating limited liquid solubility. Under his conditions, the aluminum-rich layer was reported to contain 1.91 per cent Pb and the lead-rich layer, 0.07 per cent Al. Subsequently, Pecheau2 found that in aluminum-rich alloy melts with more than 10 per cent Pb three layers were distinguishable. He reported that the middle layer contained from 3 to 10 per cent Pb. He also found that the melting point of aluminum appeared to be lowered slightly by the addition of lead. Gwyer3 investigated these alloys and found evidence of a slight lowering of the freezing point of aluminum by the addition of either lead or bismuth. He found no evidence of solid solubility in either case and made no attempt to determine the liquidus curves. Hansen and Blumen-tha14 reported that the addition of lead distinctly lowered the solidification point of aluminum. They also found that bismuth lowered the melting point of aluminum. Guillet5 reported almost complete mutual immiscibility for the aluminum-bismuth alloys in the liquid state. Bohner6 examined the effect of various concentrations of lead and bismuth on the electrical conductivity of aluminum. He found decreases in conductivity on annealing at 500&apos; C. as compared with the conductivity of the same alloys on annealing at 300&apos; C.

Jan 1, 1939

By L. W. Kempf, K. R. Van Horn

DURING the recent development of aluminum alloys for free-cutting screw-machine rod, it became desirable to know something of the solubility of lead and bismuth in liquid aluminum and in some aluminum alloys. The literature is not particularly helpful in supplying this information. These portions, therefore, of the constitutional relationships of aluminum-bismuth and aluminum-lead alloys were investigated by thermal analysis and by chemical analysis of samples taken from aluminum-rich melts in equilibrium with precipitated lead or bismuth. The solubility of lead and bismuth in some liquid aluminum-copper alloys was also investigated. Some consideration was also given to the solubility of these elements in solid aluminum. Among the earliest investigators of the aluminum-lead and aluminum-bismuth systems was Wright,1 who reported that melts of aluminum and lead formed two layers indicating limited liquid solubility. Under his conditions, the aluminum-rich layer was reported to contain 1.91 per cent Pb and the lead-rich layer, 0.07 per. cent Al. Subsequently, Pecheau2 found that in aluminum-rich alloy melts with more than 10 per cent Pb three layers were distinguishable. He reported that the middle layer contained from 3 to 10 per cent Pb. He also found that the melting point of aluminum appeared to be lowered slightly by the addition of lead. Gwyer3 investigated these alloys and found evidence of a slight lowering of the freezing point of aluminum by the addition of either lead or bismuth. He found no evidence of solid solubility in either case and made no attempt to determine the liquidus curves. Hansen and Blumenthal4 reported that the addition of lead distinctly lowered the solidification point of aluminum. They also found that bismuth lowered the melting point of aluminum. Guillet5 reported almost complete mutual immiscibility for the aluminum-bismuth alloys in the liquid state. Bohner6 examined the effect of various concentrations of lead and bismuth on the electrical conductivity of aluminum. He found decreases in conductivity on annealing at 500° C. as compared with the conductivity of the same alloys on annealing at 300° C.

Jan 1, 1938

By Charles M. Ryder

IN presenting this paper to the Institute I beg to mention, first, the results which I have obtained and the apparatus which I have employed, and to follow this with a brief description of the steps by which I have perfected this process. My present mode of testing is as follows : I obtain, either from the furnace or from the finished product in any stage in which it may chance to be, a small test-piece, usually about 4 of an inch square by 3 1/2 inches in length. I place this test-piece upon the poles of an ordinary electro-magnet, for about one minute, and thus magnetize it to its extreme limit. I then place it upon an indicator (which I will shortly describe), on which indicator there is already placed a piece of steel of similar form which has been magnetized in the same manner, the percentage of carbon of this second piece being definitely known. I then, by means of a scale, which forms part of the indicator, marked in degrees of carbonization, read the exact percentage of carbon contained in the piece under examination. My apparatus consists of an ordinary electro-magnet, connected with a suitable battery of moderate power, by which I magnetize the pieces as before described, and of an indicator which consists of a magnetic needle suitably mounted or suspended, so that it is free to deviate a few degrees only from the zero point, and having a rest, which is used to check the vibrations when in use, and to support its weight when not in use. At a right angle to the natural position of the needle I have a scale about 3 feet long, the zero point of which coincides with the natural position of the needle. This scale is marked in each direction from the zero point in degrees of carbonization. The marking of the scale is in accordance with the following rule: Taking the carbonization of the steel as a basis, I maintain the same proportion between the squares of the distances on the scale as exists between the percentages of carbon in the steel, for instance, if .08 of

Jan 1, 1877

By H. Kobbè William

ARTHUR KNAPP, Ardmore, Pa. (communication to the Secretary*).¬On p. 2275 I find a quotation from Mr. Thompson regarding the fountains of the Baku field. I have seen a large number of these gushers or fountains. In every case where unusual amounts of sand were produced the wells caved in and shut off in a few clays and were an absolute loss Very often the formation had caved so far up as to allow the water to enter the oil strata, and not only was the well lost but the ground for many acres around the well was useless for drilling purposes because the disturbed ground had allowed the gas and oil to dissipate and the water to enter. On p. 2268, Mr. Thompson is again quoted regarding the Balakhany field. If the text is consulted further, it will be found that the oil at Balakhany is heavy only in contradistinction to the Bibi Eibat, field. The gravity of the oil at Balakhany is from 28 to 32. Also, it must be noted that the illustration is taken from the conditions in the older part of the field. This field was first chilled 40 years ago, and was a worn-out field 15 years ago. The wells which produce sand are wells in which the casings are practically gone and the formations are full of water. The sand must be bailed from these wells because the clays from the upper stratum have caved into the wells and are obstructing the passage of oil. On p. 2262 is the statement that the Russian wells cannot be pumped on account of the large amounts of free sand produced. They have never tried pumping in the Baku field to any extent. Wherever tried, it has proven a great success. If we take the author&apos;s theories as correct and wish to put them into practice, it would first be necessary to consider a few figures. Let us assume that we produce oil and sand together in the proportion in which they exist in the productive strata. It is not uncommon to have wells in the California field which are not gushers, but which, by pumping, produce 1,000 bbl. per clay the first 100 clays.

Jan 3, 1917

By L. W. Kemph, K. R. VanHorn

During the recent development of aluminum alloys for free-cutting screw-machine rod, it became desirable to know something of the solubility of lead and bismuth in liquid aluminum and in some aluminum alloys. The literature is not particularly helpful in supplying this information. These portions, therefore, of the constitutional relationships of aluminum-bismuth and aluminum-lead alloys were investigated by thermal analysis and by chemical analysis of samples taken from aluminum-rich melts in equilibrium with precipitated lead or bismuth. The solubility of lead and bismuth in some liquid aluminum-copper alloys was also investigated. Some consideration was also given to the solubility of these elements in solid aluminum. Among the earliest investigators of the aluminum-lead and alunlinum-bismuth systems was Wright,&apos; who reported that melts of aluminum and lead formed two layers indicating limited liquid solubility. Under his conditions, the aluminum-rich layer was reported to contain 1.91 per cent Pb and the lead-rich layer, 0.07 per cent Al. Subsequently, Pecheau2 found that in aluminum-rich alloy melts with more than 10 per cent Pb three layers were distinguishable. He reported that the middle layer contained from 3 to 10 per cent Pb. He also found that the melting point of aluminum appeared to be lowered slightly by the addition of lead. Gwyer3 investigated these alloys and found evidence of a slight lowering of the freezing point of aluminum by the addition of either lead or bismuth. He found no evidence of solid solubility in either case and made no attempt to determine the liquidus curves. Hansen and Blumen-tha14 reported that the addition of lead distinctly lowered the solidification point of aluminum. They also found that bismuth lowered the melting point of aluminum. Guillet5 reported almost complete mutual immiscibility for the aluminum-bismuth alloys in the liquid state. Bohner6 examined the effect of various concentrations of lead and bismuth on the electrical conductivity of aluminum. He found decreases in conductivity on annealing at 500&apos; C. as compared with the conductivity of the same alloys on annealing at 300&apos; C.

Jan 1, 1939

By John C. Sawyer

A brief review is given to show that catastrophic oxidation of stainless steel in the presence of lead oxide is similar in many respects to catastrophic oxidation as caused by MoO3 and V2O5, Experimental data are presented to show that lead oxide accelerates the normal oxidation process of stainless steel by chemically altering the normally protective oxide film formed on the base metal. Data are given to show that similar reactions occur during oxidation of stainless steel in the presence of MOO3,and V2O5. THE mechanism by which pure metals oxidize at high temperatures has been the subject of intensive research for many years and much has been accomplished towards understanding the processes involved. The mechanisms by which alloys oxidize have also been investigated, but due partly to the fewer number of investigations and partly to the complexity of the oxide systems present, available knowledge is not as extensive as with pure metals. When oxidation processes are further complicated by atmospheres contaminated with sulfide, halide, or oxide vapors, the knowledge of fundamentals becomes meager or altogether lacking. Thus, it is not surprising to find that the catastrophic oxidation of stainless steels in metal oxide vapors of MOO, and V2O5 is not a well understood phenomenon despite the fact that a number of investigations have been undertaken. The literature in dealing with the subject of catastrophic oxidation is primarily concerned with the effects of MOO3 and V2O5, but does mention that other metal oxide vapors, one of which is lead oxide, appear to promote a similar type of accelerated oxidation. While this latter effect is virtually unknown, the deleterious effect of lead oxide is of considerable commercial importance, as it is believed to be one of the fundamental reasons for exhaust-valve failure in gasoline engines. For this reason studies have been in progress for many years attempting to better understand the mechanism involved. Modern exhaust-valve alloys"2containing 20 to 25 pct Cr plus nickel and/or manganese are in effect high-grade austenitic stainless steels exhibiting ex- cellent oxidation resistance in air at exhaust valve operating temperatures of 1100° to 1700°F; yet these same alloys are prone to corrode during engine service because of the conditions attending their operation. These conditions are such that the valves become coated with deposits of complex lead compounds mainly derived from gasoline additives of tetraethyllead, ethylene dibromide, and ethylene dichloride. Literature searches3-7 and discussions with various investigators show that considerable difference of opinion exists as to the nature of the lead-bearing deposits found on the surface of exhaust valves and the atmospheres to which they are subjected; yet, all seem to generally agree that corrosion, a gradual transformation of alloy to nonmetallic products of corrosion, is a consequence of the presence of lead compounds. This majority opinion seems to be substantiated by laboratory engine tests which show that corrosion does not occur to any appreciable extent when lead-free fuels are used. The first observations of catastrophic oxidation reported in the literature were probably made by pfeil,8 but it was Leslie and Fontana9 who undertook the first detailed study of the phenomenon. Their work was chiefly centered on the acceleration of oxidation which took place when stainless steels containing more than 3 pct Mo were heated in air with restricted circulation. These investigators reported that the presence of other oxides near the surface would further accelerate the rapid oxidation which occurred. While they recognized that the effect was attributable to the presence of molybdenum, it was Rathenau and Meijering" who emphasized the fact that the presence of molybdenum in the alloy was incidental to the presence of MOO3 vapor in the atmosphere surrounding the specimens. Evans,11 as well as Cunningham and Brasunas 12 studied similar

Jan 1, 1962

By T. D. Murphy, G. V. Henderson

The element silicon, with its usual partner, oxygen, plays the same role relative to inorganic materials as carbon and hydrogen play with respect to living organisms. The crystallographic structure of silicon dioxide (SiO2) consists of one atom of silicon well-nigh inseparably bonded to four contiguous atoms of oxygen, a gas of but slightly more than half its atomic weight, forming a three-dimensional network of SiO4 tetrahedra (Dietz, 1968). This wispy arrangement is the fabric of the mineral quartz which is one of the harder, more abrasive, and chemically stable raw materials to be found in Mother Nature&apos;s cupboard. Most of us are vaguely familiar with the observation that nearly 60% of the lithosphere to an approximate depth of 10 miles is composed of these two elements, which proportion actually rises to about 75% if the atmosphere, hydrosphere, and biosphere are included (Parker, 1967). Elemental silicon is a brittle steel-gray metalloid with a density of 2.42 and does not occur in nature. In its limited commercial form, which is still brittle and metallic in appearance, its density drops to 2.33. It combines with oxygen to form the gaseous oxide SiO, or the solid dioxide Si02 (analogous to its congener carbon in CO and CO2); a tetrachloride SiCI4 (analogous to CC14); or, combining with oxygen and one or more metal ions, forms the largest rock-making family of all, the silicates. Further, next to the feldspars, quartz is the most abundant known mineral and, in some form or another, accounts for roughly 12% of surficial terrestrial rock. It is this so-called "free silica" to which your attention is chiefly directed in this chapter. In any such consideration of silica, its several crystalline phases with their attendant differing physical properties appear worthy of delineation. Alpha quartz is the only one of this interesting polymorphic family that is thermodynamically stable at normal pressures and temperatures up to about 573°C. The low phases of tridymite and cristobalite can exist in the so-called metastable state below 117° to 200ºC but seldom occur in nature in these two different crystal forms (Sosman, 1965). Opaline silica, now considered by most researchers to be a variety of cristobalite, occurs in abundance and is the only exception. The three remaining polymorphs, keatite, coesite, and stishovite, also are metastable under ambient conditions. Keatite, however, is not known to occur naturally and has only been synthesized in the laboratory. The other two have been identified in submicron sizes and in microscopic amounts, occurring naturally as a result of high order shock-wave pressures generating quite elevated temperatures --such as might accompany the impact of a large meteorite on a hard sandstone terrain (Chao et al., 1962). An intriguing characteristic of these silica minerals, and one which has very practical applications, is their extremely variable densities. The classic 2.65 specific gravity of alpha quartz drops to 2.20 in tridymite, cristobalite, and lechatelierite (natural silica glass), as well as in many man-made glasses of commerce which are merely noncrystalline or amorphous solids in the form of super-cooled liquids which can no longer change their shapes (Pauling, 1950). It rises again to 2.50 and 2.93 for keatite and coesite, respectively, and finally becomes a reported 4.35 for stishovite-nearly a 50% range in density for the known physical combinations that silica naturally assumes (Frondel, 1962; Konnert et al., 1973; Pecora, 1960). Pursuing its esthetic aspects, briefly, silica is well-represented among gem stones which, to qualify as such, must have the attributes of beauty, durability, and rarity (Jahns, 1983). As quartzose gems usually have but one or, at

Jan 1, 1983

The early records of coal in Kentucky by Walker and Gist have already been mentioned. Thomas Hutchins was aware of it in 1778, or perhaps several years earlier, as in writing of the Buffaloe, now Green, River, he said, "several persons who have ascended this River, say, that Salt Springs, Coal, Lime and Free Stone etc. are to be found in a variety of places."1 The next record found is an entry to Ellis and Marshall, of 878 acres on Coal Bank Creek, in the, then Fayette County on July 14, 1784.2 The settlement might have been made, or the name given, some time before. Hermeline, in 1783, mentioned iron ore and coal on the Green River,&apos; although he had not been west of the Susquehanna River; his knowledge of coal might have come from Hutchins, although the latter made no mention of iron in that locality. In November 1790, coal was mined on Sturgeon&apos;s Creek in Lee County and floated in three barges down the Kentucky River to Cleveland&apos;s Ferry, where it was hauled to Lexington. The results were not equal to the expectations, and it was 1793 before the experiment was. repeated 4 In 1791, the estate of Samuel Wharton advertised for sale 31,000 acres "in the county of Jefferson, on the North Side of the Green or Buffaloe river, in the State of Virginia."5 In November 1795 three patents were issued for land in the then Lee County, aggregating 130,000 acres. These patents cover much of Harlan County. The descriptions of these surveys mention passing stone coal. on Rough Branch of Martin&apos;s Fork, a "great deal of stone coal" on Blacksnake Branch of Pucketts Creek, and "a quantity of stone coal" probably on Crummies Creek.6 Jedediah Morse, in The American Gazetteer, 1798, said that in Kentucky "in many places there are appearances of potter&apos;s clay, and coal in abundance." It is possible that shipments may have been made from near

Jan 1, 1942

By Frank Wartman

RECENTLY Horace Freeman1 obtained a patent on a successful method of conducting a roasting procedure described as to general features by Carl Schnabel2 almost forty years ago. Essentially, the Freeman process of roasting consists in introducing the finely powdered sulfide mineral, suspended in air or any other suitable gaseous medium, into the upper portion of a heated chamber. The stream of suspended particles is directed vertically downward. A counter-current stream of gas introduced at the bottom of the chamber flows upward. The mineral particles are oxidized as they fall through the heated atmosphere of the chamber. All air required for the oxidation may be admitted either at the top or the bottom of the chamber, or may be divided between the top and bottom inlets in any desired proportion. Heat may be recovered by passing the gases leaving the furnace through a waste-heat boiler or other form of interchanger. In speaking of the results obtained in roasting pyrite, Freeman says:3 Steam yield from the boiler exceeds 1 pound of steam per pound of pyrite con-sumed, which pays the cost of operation of the burner. The oxide produced is in the form of fused particles or hollow shells of magnetite, containing about 65 per cent of iron. It contains the gangue material ordinarily produced in flotation concentrate, of course, but it is being found that most of this can be eliminated by magnetic separa-tion, and that the sulfur content, as consistently produced, is below 0.2 percent. This material is especially interesting as a high-grade iron ore, free from phosphorus and low in sulfur. It may be sintered or briquetted. It is even more interesting as a raw material for sponge-iron production, to be directly smelted in electric furnaces without the usual cooling of the iron powder and magnetic separation between the reducing kiln and the electric furnace.

Jan 1, 1933

By M. Murakami, Y. Murakami, O. Kawano

The formation and growth of Guinier-Preston zones in Al-Zn alloys containing 4.4, 6.8, 9.7, and 12.4 at. pct zn have been studied by the X-ray small-angle scattering method. Particular attention was paid to the effects of small amounts of third elements silver, silicon, and magnesium on the formation and growth of G.P. zones. It was noticed that an appreciable number of G.P. zones were formed during the course of rapid cooling and that the size, volume fraction, and number of these G.P. zones were influenced by the existence of the third elements. During subsequent aging it was also found that the addition of both silver and silicon lowered the temperature for the growth of G.P. zones, whereas the addition of magnesium raised it. These results were explained in terms of the mutual interactions among zinc atoms, vacancies, and the third elements. A number of studies on the formation and growth of Guinier-Preston zones in Al-Zn alloys have been reported.1-4 Panseri and Federighii have found that the initial stages of zone growth take place at temperatures as low as around -100°C. For investigation of the mechanism of the initial stages of zone growth, growth studies must be carried out at low temperatures. In order to investigate the possibility of the formation of G.P. zones by the nucleation mechanism or the spinodal decomposition during quenching which was reported by Rundman and Hilliard,5 the examination of the as-quenched structure must be performed. In this paper the investigation of the early stages of the formation and growth were determined by means of the X-ray small-angle scattering method. With this technique, change of X-ray scattering intensities was measured while quenched specimens were heated slowly from liquid-nitrogen temperature to room temperature. At as-quenched state and after heated to room temperature, investigation of zone size, volume fraction, and zone number per unit volume was carried out. Measurements on these specimens yielded information on the early stages of zone formation and growth. Measurements were made also on specimens quenched to and aged at room temperature. From these measurements the previously reported model6 for the later stages of growth is confirmed; namely, the larger zones grow at the expense of smaller ones. Three elements, silver, silicon, and magnesium, were chosen as the third elements for the following reasons: Silver. In the binary A1-Ag alloy the spherical disordered 77&apos; zones were observed immediately after quenching.7 Therefore, in the Al-Zn-Ag alloys, it is suggested that silver atoms might induce cluster formation during quenching. Also, since the migration energy of the zinc atoms was found to be raised by the addition of silver atoms,&apos; silver atoms may have a great effect of the zinc diffusion, especially during low-temperature agings. Silicon. The effects of the addition of silicon atoms were found to be marked, especially at low-tempera-ture aging. In the binary Zn-Si system, no mutual solid solubilities between silicon and zinc9 and no in-termetallic compounds10 are reported to exist. Shashkov and Buynov11 investigated the behavior of silicon atoms in Al-Zn alloys and showed that silicon was not in the G.P. zones. The interaction between silicon atoms and vacancies is strong enough to increase the quenched-in vacancy concentration.* Magnesium. Magnesium atoms are reported to trap quenched-in vacancies and after much longer aging times these trapped vacancies will become free and act as diffusion carriers.13 Therefore at intermediate aging times, the diffusion of zinc atoms in Al-Zn-Mg alloys will be slower than in the binary Al-Zn alloys, whereas at longer times zinc diffusion will become faster. EXPERIMENTAL PROCEDURE The alloys used in this investigation had compositions of 4.4, 6.8, 9.7, and 12.4 at. pct Zn with or without 0.1 and 0.5 at. pct Ag, Si, or Mg. The alloys were prepared from high-purity aluminum, zinc, silver, silicon, and magnesium, with each metal having a purity better than 99.99 pct. The analyzed composition of the specimens is given in Table I. The measurements of the X-ray small-angle scattering were carried out with foils of 0.20 mm thick. The change of the scattering intensity was always measured at the fixed scattering angle of 20 = 2/3 deg. This angle exists nearly on the position of the intensity maximum. The value of the interparticle interference function14 which has large effect in this range of angles may not change abruptly in the case of the spherical shape of small zones. Therefore, from the above considerations, it is concluded that an increase of the intensity measured at this constant angle corresponds to an increase of the average radius and volume fraction of G.P. zones. The specimens were homogenized at 500°, 450°, and 300°C for 1 hr in an air furnace. For the study of the formation and growth at low temperatures, the foil

Jan 1, 1970

By Howard Hughes

IN drilling for water and oil to reasonable depths through the generally soft yielding clay and sand formation of the Coastal Plain of Texas, . Louisiana, and Mississippi, the rotating method of drilling was adopted, principally on account of the easy and quick penetration, and the low cost of the drilling plant. In favorable ground, free of heavy gravel and rock strata, as much as 1,000 ft. has been drilled in less than 36 hr., although such performances were of course rare. Hydraulic rotary drilling, or, as it is now called, rotary drilling, was used in the above States as early as 1880. The plant consisted of an ordinary derrick, a 25-h.p. boiler, a small hoist, a steam pump, and a water swivel with hose attachment, and an ordinary flat diamond-pointed bit. The successful drilling in of a phenomenal oil well by this process on Spindletop, near Beaumont, Texas, on Jan. 10, 1901, and the ascertained impracticability of drilling subsequent wells in the same locality by other methods (owing principally to heavy quicksand under pressure from below), brought rotary drilling into great prominence, practically to the exclusion of any other process throughout the Coastal Plain, and later on elsewhere. The method, as its name implies, involves the rotation of a pipe by means of machinery placed on the derrick floor. A drill bit attached to the lower end cuts a clearance for the drill pipe, with much the same motion and effect as an auger. Water forced through the drill pipe by means of a pump, and escaping through the bit, removes the cuttings and returns to the surface outside the drill pipe. In this manner the hole is kept open, permitting the drill stem to rotate freely. The pressure of the column of muddy water holds up the walls of the hole until it has been cased. Practically all the wells of the Gulf coast region, numbering nearly 10,000, have been drilled with this system. During the last five years its use has been extended to many other States and countries.

Jan 3, 1915

By B. M. Bird

ONE of the problems studied by the U. S. Bureau of Mines in cooperation with the University of Washington has been the re-treatment of table middlings. Hydraulic classification has given the best results. Instead of using the classifier to prepare the feed to the tables, as has been the practise for many years in ore dressing, it is used to separate part of a middling product that cannot be re-treated successfully on the table. Middlings are desirable in a table plant because the separation according to specific gravity is incomplete; that is, in the products of the table there is always an overlapping of free particles of coal and refuse that can be distinguished with heavy liquids such as are used in the float-and-sink test. The causes of this overlapping may be divided into two groups, those outside the table separation itself and those inherent in the table separation. The first of these groups includes, among other causes, the following: (1) poor adjustments of the table, (2) overloading or underloading the table, (3) irregularities in the quantity and quality of the feed, (4) irregularities in the power and water supply, and (5) a vertical danc-ing motion of the table deck due to weak foundations. These causes of overlapping are largely unnecessary in a properly designed and constructed plant; but whenever they are present they materially affect the character of the middling product, and hence the problem of re-treatment. The other group includes three additional causes: (6) small differences in specific gravity between coal and impurities, (7) a size-specific-gravity relationship of the coal and refuse particles in the table feed such that the sizing action of the table opposes the separation according to the specific gravity, and (8) shapes of particles that prevent a separation. The sixth, small differences in specific gravity, may be a very important reason for an incomplete separation. The change in specific gravity from coal to shale is always gradual and the designation of one part as coal and another part as refuse is arbitrary. If some specific gravity, such as 1.45, is chosen as the dividing point between washed coal and refuse,

Jan 1, 1928

By L. W. Kempf

DURING the recent development of aluminum alloys for free-cutting screw-machine rod, it became desirable to know something of the solubility of lead and bismuth in liquid aluminum and in some aluminum alloys. The literature is not particularly helpful in supplying this information. These portions, therefore, of the constitutional relationships of aluminum-ismuth and aluminum-lead alloys were investigated by thermal analysis and by chemical analysis of samples taken from aluminum-rich melts in equilibrium with precipitated lead or bismuth. The solubility of lead and bismuth in some liquid aluminum-copper alloys was also investi-gated. Some consideration was also given to the solubility of these elements in solid aluminum. Among the earliest investigators of the aluminum-lead and aluminum-bismuth systems was Wright,1 who reported that melts of aluminum and lead formed two layers indicating limited liquid solubility. Under his conditions, the aluminum-rich layer was reported to contain 1.91 per cent Pb and the lead-rich layer, 0.07 per cent Al. Subsequently, Pecheau2 found that in aluminum-rich alloy melts with more than 10 per cent Pb three layers were distinguishable. He reported that the middle layer contained from 3 to 10 per cent Pb. He also found that the melting point of aluminum appeared to be lowered slightly by the addition of lead. Gwyer3 investigated these alloys and found evidence of a slight lowering of the freezing point of aluminum by the addition of either lead or bismuth. He found no evidence of solid solubility in either case and made no attempt to determine the liquidus curves. Hansen and Blumen-thal4 reported that the addition of lead distinctly lowered the solidifica-tion point of aluminum. They also found that bismuth lowered the melting point of aluminum. Guillet5 reported almost complete mutual immiscibility for the aluminum-bismuth alloys in the liquid state. Bohner6 examined the effect of various concentrations of lead and bis-muth on the electrical conductivity of aluminum. He found decreases in conductivity on annealing at 500° C. as compared with the conductivity of the same alloys on annealing at 300° C.

Jan 1, 1938

By R. L. Skaggs, R. A. Molsberger

DARKEN1 has pointed out that in most binary liquid metal systems the thermodynamic behavior is relatively simple in the terminal regions. Between the terminal regions. the thermodynamic behavior is more complex. To describe this behavior. he has defined the stability and the excess stability as shown: Qualitatively, an inflection in the free energy of mixing curve results in a change in sign, from positive to negative, of the stability function and is associated with a phase separation. Conversely, a large, positive stability over a narrow composition range is indicative of compound formation. Darken has shown a number of binary systems where the excess stability is constant in the terminal regions and varies sharply in between. The work described in this communication was undertaken to study the variation of stability and excess stability in a binary system as a function of temperature. In addition, this work provides means for the direct comparison of previously existing equilibrium (activity) and calorimetric (molar heat of mixing) data on the Hg-Sn system. Hildebrand2 measured the vapor pressure of mercury over Hg-Sn alloys at 595°K. Calorimetric studies were made by Kawakami3 at 523°K and by Kleppa4 at 423°K. In this work, the equilibrium vapor pressure of mercury was measured over a series of Hg-Sn alloys at 453" and 503°K by use of fused salt manometer with one arm exposed to mercury vapor. Deflections of the fused salt manometer were balanced by argon pressure on the other arm. Argon pressure was subsequently measured with a dibutyl phthalate manometer. Tin activities were determined by graphical integration of the Gibbs-Duhem equation making use of the familiar Darken5 a function. The activities of mercury and tin showed positive deviation from Raoult&apos;s law at 453 and 503°K as Hildebrand observed at 595 K. In Fig. 1 are plotted log activity of mercury and tin vs reciprocal temperature. The plot contains activities obtained from calorimetric studies. Hult-gren6 has calculated activities from Kleppa&apos;s4 data, and Kubaschewski7 has similarly treated Kawakami&apos;s7 data. Presumably. in each case a regular solution was assumed. For regions where a two-phase field

Jan 1, 1970

By F. R. Cattoir, R. W. Kimball, C. T. Anderson

ONE of the principal impurities in all steels is sulphur. Sulphur-bearing, manganese-free steels exhibit hot shortness. Manganese is added to steel to improve the hot-working properties. If no sulphur were present in steel, it is probable that hot shortness would be nonexistent. This paper is the first of a series to be issued by this Laboratory reporting the measurements of hot forgeability tests and the physical properties of Fe-C alloys to which additions of various alloying elements have been made. The present paper describes the results- obtained by the addition of varying amounts of sulphur to Fe-C alloys. To obtain control over residual elements in the various charges melted in the arc furnace, it was considered advantageous to use sponge iron from one source as the melting stock rather than scrap metal having an unknown history. Small amounts of unwanted alloying elements might be introduced into the charge when scrap was used, thereby influencing the results of the various heats. A sponge iron having a high silica-lime ratio was used. Ore from Sunrise, Wyo., had been reduced to sponge iron and briquetted at the Bureau of Mines sponge-iron plant at Laramie, Wyo. The briquettes were 5 in. in diam and 2 to 3 in. in thickness, and weighed about 10 lb each. The chemical analysis of the sponge iron is as follows: C, 0.67 pct; Mn, 0.10; SiO2, 4.75; CaO, 1.4; P, 0.044; S, 0.72; MgO, 0.4; A12O3, 1.1; total Fe, 87.5; Fe metallic, 79.2; and reduction, 90.5 pct. Where a reducing agent was required, crushed graphite electrodes usually were used. The charcoal available contained 0.20 pct S. An analysis of the available coke showed it to contain 0.70 pct S. Where high sulphur heats were required, elemental sulphur additions were made to the ladle. Limestone of good quality was obtained locally and had the following analysis: CaO, 53.7 pct; MgO, 0.8; ignition loss, 42.4; R2O3, 0.2; SiO2, 3.0; and P2O5, 0.014. Melting Procedure Sponge iron was melted to produce metal stock for the experimental alloys in a silica-lined, three-phase, direct-arc, size ST, Moore Rapid Lectromelt furnace with a 500 kva rating. Fig. 1 shows this furnace installation. About 25 tons of sponge iron was melted in 75 heats, averaging 927 lb of sponge iron to the heat. An addition of carbon was required to complete the reduction of a portion of the iron oxide remaining in the sponge to prevent high losses of iron oxide in the slag and a low carbon content in the resulting metal. As reducing agents in preparing the melting stock, charcoal, coke, and a carbon product resulting from the thermal decomposition of natural gas were used. The quantity varied from 20 to 60 Ib per furnace charge, with an average of 38 lb. An average analysis of the metal obtained gave 0.52 pct C, about 0.01 pct Mn, 0.070 pct P, and 0.092 pct S. The average yield of metal was 647 lb with 241 1b of slag, the sponge-iron recovery being 70 pct. The metal obtained in melting the sponge iron was cast into pigs weighing about 20 lb each to facilitate recharging into the furnace for further refining. The pouring of the pigs is shown in Fig. 2. The average power consumption for the production of the 24 tons of metal obtained was 1704 kw-hr per ton.

Jan 1, 1954

By B. A. Wilcox, A. H. Clauer

The steady-state creep of TD Nickel NL + 2 001 pct TltOz) has been studied orer the telirperatve range 325&apos; to 1100O and the stress range 15,000 to 36,000 psi. At high temperatures (aboue 0.5 T& gran-boundary slzding is the )nost znportant )node of creep deformation, and the steady-state creep rate, is, can be related to stress and temperature by: where Q = 190 kcal pev mole and n has an unusually high value of 40. A creep mechanism based on cross slip of dislocations around The O2 particles can satisfactovily explain the low-temperature (T < 0.5 T,) cveep behavior, and the follo wing relation is applicable: Q, (a) is found to decrease from 57 to 46 kcal per mole as the stress is increased from 32,000 to 36,000 psi. THERE have been a variety of theories proposed to explain the influence of dispersed second-phase particles on the yield strength and flow stress of metals, and these have been reviewed recently by Kelly and icholson.&apos; However, only several attempts2"4 have been made to develop mechanistic treatments which characterize the creep behavior of dispersion-strengthened metals, and to date these have not been fully evaluated experimentally. weertman2 and Ansell and weertman3 proposed a quantitative creep theory for coarse-grairzed dispersion-strengthened metals, based on the concept that the rate-controlling process for steady-state creep was the climb of dislocations over second-phase particles, as suggested by choeck. The theory predicted that the steady-state creep rate, <,, was proportional to the applied stress, a, for low stresses and that is a4 o for high stresses. The activation energy for creep, Q,, was equivalent to that for self-diffusion, Qs.d., in the matrix. Some limited experimental evidence in support of this theory was obtained on a recrystallized Al-Alz03 S.A.P.-type alloy by Ansell and Lenel.6 Ansell and weertman3 also developed a semiquanti-tative theory for high-temperature creep of lineg-rained dispersion-strengthened metals in order to explain their results on an extruded S:A.P.-type alloy, which had a fine-grained fibrous structure. They suggested that the rate of dislocation generation from grain boundaries was the rate-controlling process, and fitted their results to the equation: where Q, was found to be 150 kcal per mole, i.e., QC- 4Q,.d. in aluminum. Similar high activation energies for creep7-&apos;&apos; and tensile deformation" of dispersion-strengthened alloys have been observed by other investigators for S.A.P.,&apos;" indium-glass bead omosites, and Ni + A1203 alls.&apos; There is no general agreement regarding the mechanisms involved in the creep of dispersion-strengthened metals, and this is due in part to the lack of detailed studies relating the structures of crept specimens to the mechanical behavior. The present investigation on thoriated nickel was undertaken with the aim of studying the structural changes which occur during creep of a dispersion-strengthened alloy and rationalizing the observed mechanical behavior in terms of the creep structures. EXPERIMENTAL METHODS The material used in this investigation was 1/2-in.-diam TD Nickel bar, which contained 2.3 vol pct Tho,. Obtained from E. I. duPont de Nemours & Co., Inc. The final fabrication treatment by DuPont consisted of -95 pct reduction by swaging followed by a 1-hr anneal at 1000°C. Transmission and replica electron microscopy revealed that the material had a fine-grained fibered structure with an average transverse grain size of -1 p and a longitudinal grain size of 10 to 15 p. Selected-area diffraction indicated that the fiber axis was parallel to (OOl), in agreement with the results of Inman eta1." All creep specimens were vacuum-annealed at 1300°C for 3 hr prior to testing. Transmission electron microscopy showed that the only structural change due to annealing was a slight decrease in dislocation density, confirming the reported high degree of structural stability.13 Furthermore, recrys-tallization or grain growth during creep was never observed. The structure typical of uncrept material (after the 1300 C, 3-hr anneal) is shown in Fig. 1. The grain boundaries are predominantly high angle and. although some areas show a tangled cell structure, the grain interiors are relatively dislocation-free. Individual dislocations are strongly pinned by the Tho2 particles; i.e., very rarely did dislocations move within a thin foil. The grey "halos" around some of the larger particles which protrude out of the foil surface arise from contamination in the electron microscoge. The Tho, particle size ranged from -100 to IOOOA, and the distribution is shown in Fig. 2. The technique used to obtain the data in Fig. 2 consisted of dissolving the nickel matrix in acid, collecting the Tho2 particles on cellulose acetate, and measuring about 1000 particle diameters in the electron microscope. Similar results were obtained by measuring about 600 particles in thin foils, an; the average particle size was found to be 2r, = 370A. Using the data in Fig. 2 (annealed structure), the mean planar center-to-center particle

Jan 1, 1967