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I have attended these meetings, every year, since 1926 and have served on both the Pittsburgh and the National Executive Committees, so that I am fully aware - of the ruling of this organization regarding, "No Papers by Vendors". Since I am now classified as a VENDOR, I wish to express my sincere appreciation for the invitation to formally discuss these very interesting papers --all of which herald the coming of an entirely new era in the manufacture of quality steels. I also appreciate the references by Mr. Mosser and Dr. Swinkels to my first paper on the oxygen probe which was presented at the meeting of this group, here in Chicago, in 1966 and was subsequently published in the NOH Proceedings of that year. (1)

Jan 1, 1972

By Falih Ergunalp

REGULAR production of chrome in Turkey started in 1860 with the operation of the Bursa deposits (5, Fig. I). Others were discovered at Makri, near Fethiye (3, Fig. I). For 33 years Turkey remained the principal source of this mineral. While new discoveries were coming in elsewhere, Turkey's output declined until 1921, as a result of four successive wars, which ruined the economics of the country. In 1927 a revival came with the production of 18,000 tons. In that year the Société Minière de Fethiye was formed. This company now operates mines in the Vilayets of Aydin, Denizli, Burdur and Mentese, and it has reached a maximum production of between 80,000 and 90,000 tons annually. The Turkish output therefore increased from 29,000 tons in 1930 to 55,000 tons in 1931; and to 119,009 tons in 1934. The second phase in the increase in chrome production in Turkey came about in 1935, when the Government decided to reorganize and control the mineral industry of the country according to the principles of "government control" of the present regime. Up to that time the mineral resources of the country had been exploited by private concerns. In 1935, the M.T.A. (Maden Tetkik ve Arama) Institute (Institute of Mining Research and Geological Survey) was established by the Government to do the geological and geophysical survey work and discover new mineral resources for the country. Before the establishment of the M.T.A. Institute, the chief chrome-producing region was Fethiye (3 and 4, Fig. I). As a result of the extensive work of this bureau, many new chrome deposits have been discovered and are now in production. The operational field of the mineral industry was given to Eti Bank, another Government-sponsored and Government-controlled establishment. Eti Bank gradually took over the exploitation of existing mines by purchasing them from privately operated companies. Attention was first given to the Zonguldak collieries and to the different chrome deposits scattered over the country. The Guleman mines (14, Fig. 1) were developed and put in operation in 1936. Since then the bulk of Turkish chrome output has come from this mine, which yields the highest grade ore in the world (averaging 52 per cent Cr2O3). In 1939, the recently discovered chrome deposits to the north of Eskisehir went into production, yielding ore having a Cr2O3 content of 51 to 52 per cent. Today, more than ever, the efforts of both the M.T.A. Institute and the Eti Bank are concentrated on finding new deposits and placing them in operation. There are still many promising regions of the country that merit systematic surveying and prospecting for chrome ores. Thus it is probable that Turkey will continue to make noteworthy progress in chrome output. As the annual chrome production of

Jan 1, 1944

By W. S. Ayres

I AM well aware that this subject is not strictly in the line of mining engineering, yet as it is a subject with which mining engineers at times have something to do, I have thought, perhaps, it might not be wholly out of place to communicate to the Institute something of the method used in determining deflection, and of its final issue. Having felt a need of some simple formula for determining the deflection of girders of uniform cross-section under any load, I have been led through the counsel of Mr. Frederick J. Slade, to whom I am indebted for many suggestions, to undertake a labor of which I shall in this paper give only some of the most important features. The results arrived at agree with those obtainable from the received formula; of Weisbach, Rankine, and others, but the expressions given by these authors, and by all others that I have at hand, are of such a form that they are not easily applied by those whose higher mathematics have become rusty from disuse, and they require, moreover, too much labor in their application to be of practical value. The general formula that I have adopted is similar to that given by Rankine, and is deflection = [mWl3 -El], in which l is the span, W the total load, E the modulus of elasticity, I the moment of inertia of the uniform cross-section of the girder, and m a factor depending for its value on the mode of distribution of the load. The problem then is to find the value of this factor m in the formula, and for some distributions of the load it leads to a number of mathematical difficulties. In this place I shall consider first the girder to be loaded symmet-

Jan 1, 1877

By J. T. Norton, J. G. McMullin

E. R. JETTE*—The way this ternary was developed there are two directly determined points on each of the iso-thermals except the 700° isothermal, where I believe there is only one. How were the end points determined, and what was the basis for it? Whose work formed the basis for the silver copper line ? M. B. BEVER †—At most temperatures the authors determined three points of the isothermal line. For example it can be seen from Fig 3 and 4 how three points for the 600°C contour line were obtained. The authors took two additional points for each temperature from the copper-silver binary diagram contained in Hansen's volume on constitution diagrams. It is correct that the 700°C contour line is based only on one point in the ternary field which was found by a slight extrapolation of Fig 4. R. I. JAFFEE*—Are the tie lines representing phases in equilibrium parallel to the silver-copper boundary ? M. B. BEVER—Are you asking that as a matter of principle ? R. I. JAFFEE—I assumed that would follow from principle. I wonder if that is in accordance with the authors' ideas too. M. B. BEVER—I do not believe the authors obtained any information on the tie lines in the two-phase field. Of course, in the limiting case of very low gold contents the tie-lines approach to the silver-copper boundary, but generally in the two-phase field I do not think that the tie-lines have to be parallel to the boundary. E. R. JETTE—I am quite sure they do not have to be parallel. You cannot tell from this work in which direction they go. E. A. GULBRANSEN*—Were any pycnometric measurements made to check the lattice parameters of the alloys ? M. B. BEVER—I did not hear any-

Jan 1, 1950

By H. I. Smith

THE technical and safety press have devoted much space in support of or in opposition to the use of booster and auxiliary fans in coal mines. The Mine Safety Board of the U. S. Bureau of Mines has given the matter consideration, and the Mine Ventilation Committee of the A. I. M. E. is now seeking a discussion of the merits and demerits of such fans to guide it in formulating recommendations. In this paper, I will set up some principles on which I believe most engineers will agree and from which we may work toward a decision, though as to what that decision shall be there may be a difference in opinion. Before stating the points on which I believe. there is accord, I will distinguish between booster and auxiliary fans.

Jan 1, 1927

NEW YORK SECTION ALLEN H. ROGERS, Chairman, H. C. PARMELEE, vice-chairman, FOREST RUTHERFORD, Vice-chairman, W. S. DICKSON, Secretary, 71 BROADWAY, NEW YORK, N. Y. J. E. JOHNSON, JR. F. T. RUBIDGE, Treasurer, P. G. SPILSBURY A meeting of the New York Section was held at The Machinery Club on Friday evening, Oct. 4, 1918, The Chairman, Allen H. Rogers, presiding. The CHAIRMAN.-MOST of us, I suppose, have been affected more or less by The request of The Fuel Administration that we leave our automobiles standing in The garages on Sundays. We shall all be interested in hearing about The situation that has called forth This, request, and The Oil Administrator, Mr. Requa, has kindly come from Washington to Tell us about it. MARK L. REQUA.-I am very glad To Tell you about the oil problem during This war period. The United States is supplying by far The greater part of all The petroleum products consumed in Great Britain, France and Italy. In addition To This, we have had To supply a marked increase in our domestic consumption, not only of The refined products, but of fuel oil as well. The combination has put a strain on The oil industry, which it is very difficult To meet. The oil companies, being under contract, had no option as To who should get Their oil first, and They were delivering pro rata To everybody; manufacturers of furniture were getting oil with The same regularity as Those who were making aeroplanes or munitions, and The oil companies felt that something should be done. The first order with which I had. anything To do was The priority list for The delivery of fuel oil. That list contained 12 classifications, beginning with bunker fuel and railroads, and you will realize The complexity of The situation when you hear that munitions plants are in class 11. The priority list held during The winter, but transportation became so bad, because of The number of ships that were Taken for trans-Atlantic use, that some of The oil companies were not able To deliver more Than about 60 per cent. into class 5, and nothing beyond that point. To add To the Troubles, the Tank-car mileage fell off. The average for 1917 was about 36 miles per car per day. in January, 1918, it dropped To about 8 miles, and it must have been nearly zero in The early part. of February. Because of The extremely severe winter, furthermore, pipe lines were not delivering anywhere near Their normal capacity. A new priority list has recently been promulgated, introducing a few slight changes. Natural gas has been brought under its provisions, and it has been extended To include The Pacific Coast, which was not considered necessary last winter. The situation in The gas industry is not satisfactory; it is estimated that There will be a decrease of 10 To 20 per cent. in The quantity of natural gas available This winter, as compared with last winter.

Jan 11, 1918

By W. F. Domis, F. von Gemmingen, R. W. Whitmore, F. Garofalo

Constant-load creep-rupture tests at 1100°, 1300° and 1500°F were made on a Type-316, 18 Cr-8 Ni-ZMo, austenitic stainless steel to determine the relationship between ruptzire life and other aspects of creep behavior, The test program was designed on a statistical basis to check the variability of various creep properties and to determine emprically the dependence of minimutn creep rate and ruptzire life on initial stress, The dependence of the rupture life, tn, on the initial stress, a,, is found to be related to the stress dependence of the wrinimum creep rate, i,, and secondary creep strain, The instabilities or breaks found in the conventionual log - logt, plots can be traced to either a change in the linear dependence of log i, on log a, or to a change in secondary creep strain. In the alloy tested, rupture is found to be predowmanantly of the inter crystalline type, For this material, the secondary creep strain is -found to depend on the nature of the grain boundary precipitate, which affects grain boundary migration. It has been shown for a variety of metals and al tested at elevated temperatures under creep conditions that the empirical relationship exists between rupture life, tr, and minimum creep rate, i,. This relationship, in which C and a are in some cases independent of stress or temperature, shows in a general way that creep rupture depends on creep behavior prior to tertiary creep stage. To determine more fully the factors which control creep rupture requires, therefore, more knowledge of the relationship between rupture and creep behavior. To obtain such information, constant-load creep-rupture tests have been made on a Type-316, 18 Cr-8 Ni-2 Mo, austenitic stainless steel at 11000, 1300°, and 1500°F. These tests were designed on a statistical basis to determine the variability of the various creep properties measured and to determine empirically the stress dependence of minimum creep rate and rupture life. As a result of this work, various empirical relations have been established defining more closely the factor, C, in the relation between rupture life and minimum creep rate. This factor is found to be proportional to the amount of strain during secondary creep. The variation of secondary creep strain with rupture life and temperature is determined and its effect on rupture behavior discussed. The variability in minimum creep rate and rupture life is also dis- cussed and the dependence of these quantities on initial stress is interpreted. TEST MATERIAL AND TEST PROCEDURES The material tested is an austenitic stainless steel, AISI Type 316, of the following composition: C, 0.07 pct; Mn, 1.94 pct; P, 0.01 pct; S, 0.021 pct; Si, 0.38 pct; Cr, 18 pct; Ni, 11.4 pct; Mo, 2.15 pct; All 0.003 pct and N, 0.043 pct. The material was received as a hot-rolled 0.5-in. diam bar which was sectioned into 3.25 in. long blanks. Each blank was heat treated by holding 1/2 hr at 2000° F followed by water quenching. A 3/8-in. coupon was removed from each heat-treated blank and the microstructure was examined, the grain size determined, and the hardness measured. The microstructure was found to be uniform from blank to blank and the grain size was found to range from 4 to 6 ASTM numbers. Hardness, measured using a 20-kg load, varied between 127 and 148 Vpn. Tensile creep-rupture specimens having a 0.25 in. diam within a 1.5-in. reduced section were machined from the heat-treated blanks. Constant-load tests were made on these specimens at 1100°, 1300°, and 1500 F. Six specimens were tested at each stress level. Three creep-rupture machines were employed for tests at each temperature, two specimens being tested in each machine for each stress level. To minimize any effect due to local inhomogeneities along the length of the as-received bar the specimens were randomized before test. Each specimen was tested to rupture and in most cases an autographic extension-time curve was obtained. For very low stress levels at 1500°F no auto-

Jan 1, 1962

By L. D. Jaffe

From the limited experimental data in the literature, preliminary values were derived for the thermal diffusivity of titanium alloys and for the quenching severity of various mediums used in heat treating them. The thermal diffusivity, under quenching conditions, was found to be approximately 0.006 sq in. per sec. The quenching severity H for brine is approximately 8, for water 4, for oil 0.9, for air 0.08, and for argon 0.02 in. -' The quenching severity of the Jominy-Boegehold end quench water jet against titanium alloys appeared effectively infinite. Using these results, graphs were prepared showing ideal round sizes and Jominy positions having cooled conditions equivalent to those at the center and surface of titanium alloy rounds, plates, and sheets quenched in various media. THE importance of proper quenching of steel parts has long been recognized, and much quantitative work has been done on the subject. Recently, it has become evident that for titanium alloys, too, the rate of cooling from high temperature is important in obtaining high strength and hardness. Maximum hardness and strength may not be attained in the as-quenched condition but rather after a subsequent tempering or aging treatment. Nevertheless, if cooling from temperatures near the ß transus is too slow, for the hardenability of the alloy used, a soft a-ß structure will be produced which will not harden on subsequent aging.'-" The quenching of parts of practical interest can usually be approximated by simple shapes, such as cylinders (rounds) and plates (or sheets) of various thickness and combinations of these. A standard that has been used extensively for comparison purposes is the center of an ideal round: a cylinder quenched in a medium that instantly cools its surface to room temperature." For steel, considerable practical use has been made of the Jominy-Boegehold end quench hardenability specimen,".' and its value for titanium alloys is becoming evident. It therefore appeared worthwhile to attempt comparison of cooling conditions in titanium alloy rounds and plates of various sizes quenched in various media with cooling conditions in ideal round and Jominy quenches. These comparisons are based upon measurements reported in the literature. Quenching Severity of Jominy Water Jet and of Brine As one starting point, there were available the data of Phillips and Tobin8 for positions on a Jominy specimen having the same hardness as the centers of round bars of various size quenched in 5 pct NaOH brine, shown in Table I. The Jominy speci- men is a round bar, normally 1 in. diam and 4 in. long, quenched by a water jet at one end and air cooled on the other surfaces.' After quenching, hardness is measured vs distance from the quenched end on longitudinal flats ground 0.015 to 0.10 in. deep. The data of Table I were based on a subsized specimen of 3/4 in. diam. Since the positions tested are close to the jet quenched end, cooling there may be taken as due solely to the jet, and air cooling can be neglected. These positions are then equivalent to various locations near one surface of an 8 in. plate jet quenched on both sides. Assuming that the thermal diffusivity is constant and that Newton's law of cooling holds, temperature vs time curves at corresponding positions in Jominy specimen and round bar then may be calculated for various assumed quenching severities of the water jet and of the brine. Cooling curves are generally taken to be metallurgically equivalent when they show the same time to reach a temperature halfway between the initial (heat treating) temperature and the final (quenching medium) temperature.5 On this basis, using Russell's tables,9 upplemented by heat flow tables derived in similar fashion by the author for positions near the surface of severely quenched plates, it was found that the experimentally observed equivalence, Table I, was best matched if the quenching severity H of the Jominy water jet was taken as infinite (H = co). This means that the jet quenched surface should be considered as instantly cooled to the temperature of the water

Jan 1, 1956

By P. R. Celmer, Leonard R. Weisberg

THE principle of fractional crystallization has been successfully used to prepare high-purity (99.999 pct) Ga. Hoffman and Scribnerl removed single crystals of gallium solidifying in a gallium melt, while Zimmerman2 grew single crystals from the melt by the Kyropolous technique. In contrast, attempts at purifying gallium by zone refining have been less successful. ichards, reported that despite the passage of 40 zones through a gallium ingot, there still remained 5 to 70 ppm each of Cu, Fe, Ca, Mg, Si, Al, and Ag. Previously, Detwiler and Fox4 detected only one impurity, Pb, segregating in zone-refined ingots. These surprising results prompted an investigation of the factors controlling impurity segregation in gallium. Possible reasons for this were insufficient diffusion of impurities in the melt; recontamination of the melt by its oxide film which is not affected by the passage of the zone; reaction of gallium with the boat; sudden freezing of gallium following supercooling, especially since gallium easily supercools to and trapping of impurities at grain boundaries. Impurity segregation tests were carried out by directionally freezing gallium using the Bridgman rnethd, modified in that the molten gallium is lowered out of a furnace into a slush of dry ice and trichloroethylene, thus minimizing supercooling. Since the gallium is contained vertically, the oxide film is in contact only with the tail end of the melt. It was found that Teflon makes an excellent crucible for gallium since it is quite pure, non-reactive, translucent, flexible, machinable, and is not wet by gallium. The gallium crystals could be grown at various speeds, and the melt could be vigorously stirred by a Teflon rod moving through the gallium in a vertical reciprocating fashion. Single crystals could be grown by placing a solid Teflon plug at the bottom of the melt drilled out in such a way to cause the solidifying gallium to follow a winding path. Thus, even if many crystals are originally nucleated, only one grain will predominate. The grain structure of the gallium crystals was revealed by an etchant composed of equal volumes of HC1, HNO3 and HF, diluted with water to half strength. Emission spectrographic analyses were carried out on samples removed from the front and tail ends of the resulting gallium ingots. Typical results of this study are summarized in Table I. The rate of freezing in all three cases was about 1 in. per hr. It can be seen that even though stirring of the melt does help, it is even more important to grow a single crystal of Ga in order to obtain good segregation of impurities. The effect of crys-tallinity on the segregation of impurities was previously observed6 in the directional freezing of germanium; however, in this case, the effect was much less pronounced. This dependence of impurity segregation on the crystalline perfection of Ga may be related to its thermal conductivity which is the most anisotropic of all metals.7 The anisotropic thermal conductivity can cause the solid-liquid interface to be nonuniform, thus leading to trapping of impurities during freeing, and therefore reduced segregation. In conclusion, it is indicated that zone refining of gallium would be more successful if seeding and similar precautions are taken to insure single crystal growth. The authors are indebted to Mr. H. H. Whitaker for the spectrographic analyses and to Drs. B. Abeles and F. D. Rosi for helpful advice and encouragement throughout the course of this work. This research was supported by the Electronics Research Directorate, Air Research and Development Command, under Contract No. AF33(616)-5029. REFERENCES 'J. 1. IToffmon and B. T. Scribrer: I. Research h'atl. Bur. Standards, 1935, "01. 15, p. 205. 'W. Zirnmerman: Science, 1954, vol. 119, p. 41. %J. L. Richards: Nature, 1956, vol. 117, p. 182. 'D. P. Detwiler and W. M. Fox: I. Metals, 1955, "01. 7, p. 205. 5P. W. Bridgman, Proc. Am. ilcod. Sci., 1925, vul. 60, pp. 305,385,423. "S. L1. Christian: private c ommuni cation. 'K. W. Powell: roy. Sac., 1951, vol. 209, p. 525. 'W. G. Pfann: Zone Re fining, p. 20. John Wiley and Sons, Inc., New York, L058.

Jan 1, 1962

By R. J. Evans, A. G. Revesz

Silicon films have been grown by chemical reaction on (111) silicon substrates. The surfaces were examined by various microscopic and interfero-metric methods. Surface structures are classified into two groups depending on whether the angles between the bounding planes and the (111) surface are small (<3 deg) or large (> I0 deg). A layer-gvowth mechanism is postulated to explain the topography and the influence of growth parameters. Growth proceeds by lateral expansion of the (111) layers in (211) directions, thereby forming steps. The step edges are perpendicular to the direction of expansion and are thus along (110) directions. Step bunching md surface nucleation both play an important role in modifying the flow pattern and in the step regeneration. These are influenced ver?) much by impurities, especially oxygen. Although the growth is a result of a surface-controlled ga: reaction, it is very similar to growth from an impure solution. OVERGROWTH ("epitaxial growth") of silicon is important and widely used. During the past years several investigators have observed various topographical features or so-called faults on the grown films. A study of the surface morphology gives some insight into the growth mechanism. I) EXPERIMENTAL Silicon films have been grown on silicon substrates by a method described by Theuerer.&apos; Silicon is formed by reduction of SiCl, in hydrogen. The rate of incidence of SiC1, was varied between 5 x 10"6 and 2 x 10&apos;4 moles min-&apos; cm-&apos;. The mole fraction of Sic4 in the Hz-SiCL mixture was about 5 x X Both the rate of incidence and the mole fraction were calculated on the assumption that the Hz bubbling through the SiC1, reached equilibrium saturation. Assuming uniform velocity distribution, the linear velocity of the gas in the reactor tube was estimated to be 2 cm sec-l. The temperature of deposition was varied between 1070" and 1260°C. Chemically polished p-type silicon wafers of 20 to 100 ohm cm resistivity were used as substrates. These were within 1/2 deg of a (111) orientation. The thickness of the grown n-type film was determined by two methods: a) measurement of the depth of the p-n junction taking into account the junction shift due to diffusion, b) measurement of the traces of stacking-fault tetrahedra on the (111) plane.&apos; The agreement between the two methods was better than 20 pct. The rate of growth varied between 0.2 and 4.0 pmin-&apos;. The formed films were examined by reflection and light-section microscopy, and by multiple-beam interferometry. Phase-contrast illumination revealed height differences of about 30A. For measuring heights greater than 1 p a light-section microscope3 was used. The resolution by multipke-beam interferometry4 was between 50 and 100A. Crystallographic directions on the surface were determined by X-ray and from the orientation of etch pits and stacking faults as revealed by Dash etch (I part HI?, 3 parts HNOJ, and 12 parts CH3COOH). Some specimens have been investigated by electron microscopy. Platinum-shadowing and carbon-replica techniques were used to show the fine topography and reflection diffraction to determine the structure of the grown layers. 11) RESULTS The topographical features can be classified into three groups. he first group is comprised of fine ridges (striations). The second group consists of structures, which are bounded by planes making angles of less than 3 deg with the (111) surface. They are, therefore, vicinal planes. Structures which closely resemble growth or etch pyramids from the third group would normally be bounded by perfect low-index crystallographic planes. In this case they are deformed. The angles between the bounding planes and the (111) surface are generally larger than 10 deg. The fine ridges are present, even on the smoothest surfaces, as shown in Fig. 1. They are along a (110) direction. The height differences could not be resolved with interferometric techniques. The basic characteristic structures of the second group are depressions and hillocks. These are bounded by three planes, two of them with larger slopes than the third one. The edges between the planes, as projected to the (111) surface, point in (211) directions. Various habits of these structures are shown

Jan 1, 1964

By Richard J. Fruehan

ThE thermodynamic activities of nickel and chromium in liquid Ni-Cr alloys have not been previously reported. There have been several investigations on the solid alloys.1-3 In the present investigation the activity of chromium in liquid Ni-Cr alloys at 1600° C was determined by the use of the following galvanic cell, The use of galvanic cells employing solid oxide electrolytes for determining the activity of metals in solid alloys was first demonstrated by Rapp and Maak4 on Cu-Ni alloys between 700° and 1000°C. Recently Schwerdtfeger5 tested the performance of the ZrO2(CaO) electrolyte at 1600°C and found it satisfactory for oxygen pressures as low as 10"12 atm. He also demonstrated the use of solid oxide electrolytes for determining the activities in liquid metal systems in measuring the activity of manganese in Fe-Mn alloys at 1500°C. Extensive investigations have been carried out in this laboratory, exploring the oxygen partial pressure lower limit at which ZrO2(CaO) electrolyte can be used satisfactorily in oxygen galvanic cells at 1600°C. In a paper to be published at a later date,9 it is demonstrated conclusively that ZrO2(CaO) exhibits insignificant electronic conductivity at oxygen pressures down to about 3 x 10"13 atm which is lower than the oxygen partial pressure in equilibrium with Cr-Cr2O3 at 1600°C. Therefore, the activity of chromium can be related to the measured reversible electromotive force of the cell in the present investigation since no electronic short circulating will occur. Fig. 1 is a schematic diagram of the cell used. The Cr-Cr2O3 electrode was made of equal weights of chromium and Cr2O3 powders which were mixed and packed into a recrystallized alumina crucible. A Pt-wire lead was embedded into the Cr-Cr2O3 compact to insure good contact. A ZrO2(CaO) crucible, supplied by the Zirconium Corp. of America, contained the Ni-Cr melt equilibrated with solid Cr2O3. The ZrO2(CaO) crucible was placed on the Cr-Cr2O3 electrode and additional Cr-Cr2O3 mixture was packed around it. Contact with the Ni-Cr alloy was made with a Cr2O3 tube, which is a weak electronic conductor. A platinum wire lead was attached to the Cr2O3 tube. The galvanic cell was lowered slowly into the hot zone of the furnace tube in order to avoid too large a thermal shock which could break the ZrO2 (CaO) crucible. The furnace was con- tinuously flushed with purified argon during the experiment. The temperature was measured with a Pt-Pt/10 pet Rh thermocouple and maintained at 1600° ± 5°C. The electromotive force was measured with a recording potentiometer. The furnace was turned off when measurements were being made in order to avoid induction effects and the reversibility of the cell was demonstrated in the usual manner. The electromotive force was measured several times over a period of approximately 1 hr. During that period the electromotive force remained constant within ± 3 pet and did not continuously drift in any one direction. After the experiment the alloys were analyzed for chromium in the usual manner. The measured electromotive forces of the cell at 1600°C, (2912°F), are listed in Table I. The activity of chromium, with solid pure chromium as the reference state, (a), was calculated using Eq. [l], , n F E I, n lna RT- U] where E is the measured electromotive force, F is the Faraday constant, and n is equal to 3, the number of equivalents per mole, (nF/RT = 18.59 volts&apos;1 at 1600°C). The resulting activities are listed in Table I. The activity of chromium relative to pure liquid chromium was also calculated. The free energy of fusion of chromium at 1600° C was calculated using

Jan 1, 1969

By John Henderson

FOR some time now the most commonly accepted description of liquid silicate structure has been the "discrete ion" theory, proposed originally by Bockris and owe.&apos; This theory is that when certain metal oxides and silica are melted together, the continuous three dimensional silica lattice is broken down into large anionic groups, such as sheets, chains, and rings, to form a liquid containing these complex anions and simple cations. Each composition is characterized by "an equilibrium mixture of two or more of the discrete ions",&apos; and increasing metal oxide content causes a decrease in ion size. The implication is, and this implication has received tacit approval from subsequent workers, that these anions are rigid structures and that once formed they are quite stable. The discrete ion theory has been found to fit the results of the great majority of structural studies, but in a few areas it is not entirely satisfactory. For example it does not explain clearly the effect of temperature on melt structure,3 nor does it allow for free oxygen ions over wide composition ranges, the occurrence of which has been postulated to explain sulfur4 and water5 solubility in liquid silicates. In lime-silica-alumina melts the discrete ion theory is even less satisfactory, and in particular the apparent difference in the mechanism of transport of calcium in electrical conduction8 and self-diffusion,&apos; and the mechanism of the self-diffusion of oxygen8 are very difficult to explain on this basis. By looking at melt structure in a slightly different way, however, a model emerges that does not pose these problems. It has been suggested5" that at each composition in a liquid silicate, there is a distribution of anion sizes; thus the dominant anionic species might be Si3,O9 but as well as these anions the melt may contain say sis0:i anions. Decreasing silica content and increasing temperature are said9 to reduce the size of the dominant species. Taking this concept further, it is now suggested that these complexes are not the rigid, stable entities originally envisaged, but rather that they exist on a time-average basis. In this way large groups are continually decaying to smaller groups and small groups reforming to larger groups. The most complete transport data 8-10 available are for a melt containing 40 wt pct CaO, 40 wt pct SiO2, and 20 wt pct Al2O3. Recalculating this composition in terms of ion fractions and bearing in mind the relative sizes of the constituent ions, Table I, it seems reasonable to regard this liquid as almost close packed oxygens, containing the other ions interstitially, in which regions of local order exist. On this basis, all oxygen positions are equivalent and, since an oxygen is always adjacent to other oxygens, its diffusion occurs by successive small movements, in a cooperative manner, in accord with modern liquid theories." Silicon diffusion is much less favorable, firstly because there are fewer positions into which it can move and secondly, because it has the rather rigid restriction that it always tends to be co-ordinated with four oxygens. Silicon self-diffusion is therefore probably best regarded as being effected by the decay and reformation of anionic groups or, in other words, by the redistribution of regions of local order. Calcium self-diffusion should occur more readily than silicon, because its co-ordination requirements are not as stringent, but not as readily as oxygen, because there are fewer positions into which it can move. There is the further restriction that electrical neutrality must be maintained, hence calcium diffusion should be regarded as the process providing for electrical neutrality in the redistribution of regions of local order. That is, silicon and calcium self-diffusion occur, basically, by the same process. Aluminum self-diffusivity should be somewhere between calcium and silicon because, for reasons discussed elsewhere,&apos; part of the aluminum is equivalent to calcium and part equivalent to silicon. Consider now self-diffusion as a rate process. The simplest equation is: D = Do exp (-E/RT) [I] This equation can be restated in much more explicit forms but neither the accuracy of the available data, nor the present state of knowledge of rate theory as applied to liquids justifies any degree of sophistication. Nevertheless the terms of Eq. [I] do have significance;12 Do is related, however loose this relationship may be, to the frequency with which reacting species are in favorable positions to diffuse, and E is an indication of the energy barrier that must be overcome to allow diffusion to proceed. For the 40 wt pct CaO, 40 wt pct SiO2, 20 wt pct Al2O3, melt, the apparent activation energies for self-diffusion of calcium, silicon, and aluminum are not significantly different from 70 kcal per mole of diffusate,&apos; in agreement with the postulate that these elements diffuse by the same process. For oxygen self-diffusion E is about 85 kcal per mole,&apos; again in agreement with the idea that oxygen is transported,

Jan 1, 1963

By D. A. Elgillani, M. C. Fuerstenau

With either sulfonate or oleate as collector, quartz responds to flotation with moderate additions of calcium only at moderately high pH, where some portion of the activator has hydrolyzed to caOH+ . Calculations of the concentrations of various ionic and precipitated species of calcium and collectors suggest that the products of [(CaOH+) (RSO3)] and [(CaOH+)(01-)] determine whether flotation is obtained under specific conditions. Ion products on the order of 10-12 were calculated for both the sulfonate and oleate systems. The activating effect of calcium ion in nonmetallic flotation systems is of considerable interest because of the normal presence of calcium in natural water. As a result, this phenomenon has received quite some attention in the past. Kraeber and Boppel1 showed that quartz could be activated by calcium above pH 10 with sulfonate as collector. The feasibility of selectively separating quartz from hematite with calcium activation at relatively high pH was demonstrated by Clemmer, Clemmons, Rampacek, Williams, and stacy.2 Cooke and Digre3 showed with a bubble pick-up method that the minimum quantity of calcium ion required as activator for complete pick-up of particles occurs at pH 11.5 for an addition of 20 mg per liter sodium oleate. They also showed that larger additions of calcium (10-fold increase per unit decrease of pH) must be added for complete bubble pick-up as the pH is reduced. Schuhmann and Prakash,4 using a vacuum flotation technique, found that quartz could be floated with moderate additions of calcium chloride and oleic acid at neutral pH, providing the metal ion was present in stoichiometric excess over the quantity needed to form the normal soap with oleic acid. They also reported that calcium will function as an activator only in basic media. More recently, Eigeles and volova5 have shown that essentially complete flotation of quartz is obtained with 6 x 10-4 mole per liter calcium chloride and 1.7 x 10-5 mole per liter sodium oleate at pH 11.6. while no flotation is obtained at about pH 10.9 and below. The importance of adsorption of activator and collector at the air-liquid interface is also demonstrated in these systems. The important role that metal ion hydrolysis assumes in quartz activation systems was also demonstrated recently.6-8 A detailed investigation of metal activation in sulfonate flotation of quartz was undertaken in one system7 and yielded a number of interesting and important observations. Quantification of the data of this system7 to the extent desired was not possible, though, because certain species could neither be ignored nor accounted for accurately. These difficulties can be circumvented when calcium is involved as activator. This detailed analysis was undertaken to obtain a more quantitative explanation of calcium and metal ion activation in quartz flotation. EXPERIMENTAL MATERIALS AND METHODS Sodium alkyl aryl sulfonate9 mol wt 450, and pure potassium oleate were used as collectors. All other reagents used were reagent grade in quality, i.e., n-amyl alcohol as frother, KOH for pH adjustment, and calcium chloride. Conductivity water, made by passing distilled water through an ion exchange column, was used in the investigation. Quartz was prepared by leaching the sized sample (48 x 150 mesh) with HC1 until no iron could be detected in the leach liquor. The experimental equipment and procedure were the same as that described previously.6,10 EXPERIMENTAL RESULTS As the presence of precipitates was noted in all of the systems to which ca++ and collector were added, experiments were undertaken to determine the solubility products of calcium sulfonate and calcium oleate using a nephelometer. With this technique, collector is titrated into a known solution, which in this case was 5 x 10-5 mole per liter CaCl2 at pH 5.5. Upon precipitation of the calcium-col lector salt, e.g., calcium oleate, light is scattered and detected

Jan 1, 1967

By C. A. Doh, R. Q. Fields, M. Lebourg

A formation tester run on logging cable is now available to the oil industry. It offers a method of safely and rapidly testing possible producing formations in uncased holes. These tests can be made up the hole after running the electric log. Reservoir pressure data is continuously recorded at the surface as the fluid sample is extracted. The tester may be assembled with a reservoir of 1-, 2.75-, or 5.5-gal capacity. A retaining pad on the body of the tool is expanded against the wall of the hole at the exact depth desired; this depth is determined by electrical log control. Two bullets are then fired through the center of the retaining pad which create a connection between the formation and a flow line to the sample chamber. When the chamber is filled, a valve is closed and the fluid sample sealed at maximum pressure. The tool is retracted to minimum diameter and brought out of the hole. Electrical circuits permit a complete recording at the surface of the mechanical operations of the tool as well as the formation pressure build-up and the hydrostatic mud pressure. The tool was introduced commercially during the latter part of 1955 in the Gulf Coasts of Louisiana and Texas. Over 1,000 operations have been made to date (Sept. 1, 1956); 50 per cent of which resulted in successful tests. Failures have been due mostly to ineffective sealing in unconsolidated sands. One major company had 41 successful tests out of 80 attempts with 23 ineffective pad seals. Results for this company were very gratifying as to pinpointing gas-oil ratios, indicating productive permeabilities and aiding in determination of fluid content where electrical log and side-wall coring information were inconclusive. Eight typical pressure curves are discussed (including misruns). Six types of fluid recoveries are interpreted. Eight actual field examples of electric logs, showing the problems solved by the formation tester, are illustrated. The present applications of the tool are discussed: 1. Determination of productive fluid—varticularlv differentiating between gas and oil. 2. Determination of reservoir pressure as an aid to: (a) safety in completion technique, (b) reduction in drilling costs, and (c) reservoir analysis. 3. Determination of minimum gas-oil ratios. 4. Location of gas-oil or oil-water contacts. 5. Recovery of samples for examination and analysis: oil (gravity); gas (hydrocarbon content); water (salinity). Additional applications envisioned for the future are also given: (I) subsurface exploration based on accurate pressure, (2) recovery of fluid samples from the undisturbed reservoir for PVT work, and (3) possible quantitative study of permeabilities or productivity index. Running the formation tester requires no special pre-cautionary measures. Because full hydrostatic mud pressure is maintained at all times, well depth is no problem. Thus, the method allows safe, economical testing in wells which heretofore could only be tested by setting casing. INTRODUCTION A new method of safely and rapidly testing possible producing formations in uncased holes is achieving considerable success. The method offers promise of further advances in reservoir study. Called the formation tester, the new instrument is unique in that it operates on logging cable. It thus offers all the advantages of wire-line operations and becomes an important adjunct to present logging and side-wall coring services. The tester is operated against the wall of the hole at any depth desired. Zones to be tested are usually determined by a study of the electrical and the micro-caliper surveys. Reservoir data, as well as the operating cycle of the tool in the hole, are continuously recorded at the surface during the operation. The tester, as it was originally designed, was capable of recovering a 1-gal sample of reservoir fluid per trip in the hole. Tools with reservoirs of 2.75- and 5.5-gal capacity are now available. The 5.5-gal reservoir is equipped with a segregating system, set before going in the hole, so that the last portion of the recovery (usually 1 gal) is automatically separated from the first portion. This makes it possible

Jan 1, 1958

By G. Wakefield, A. H. Daane, D. H. Dennison, F. H. Spedding

Preparation of pure scandium metal was accomplished by calcium reduction of the fluoride by two methods; a low-temperatzdre alloy process and direct reduction with subsequent distillation of the product. The following properties were determined: melting point: 1181OK; boiling point (calculated): 3000°K; lattice constants at 298°K (hexagonal lattice): a = 3.308 * 0.001 A, c = 5.267 * 0.003A; calculated density at 298°K, g per cm3: 2,990 + 0.007; electrical resistivity, ohm-cm: 299°K, 66.6 ± 0.2 x 10 -6; 373oK, 77.4 * 0.2 x 10 -6; thermal coefficient at 299°K, ohm-cm per deg: 5.4 X x; heat of sublimation at 298°K, kcal pel- mole: 80.79. The vapor pressure was determined as a function of temperature between 1505o and 1748°K, with the data fitted to a straight line shielding the equation: Log Pmm = -1.718 X 104/ToK + 8.298. SCANDIUM, element number 21, was first discovered by Nilson in 1879 and was recognized as the Ekaboron as predicted by Mendeleff. As it is in group III of the periodic table, the general properties are a little like aluminum and also resemble quite closely the properties of yttrium and the rare-earth metals, in both the metallic and ionic form. Although the earth&apos;s crust contains approximately 5 ppm of scandium (the element is as abundant as arsenic and twice as abundant as boron) it generally occurs so widely distributed that it has earned the reputation of being very rare. The one exception to this is the mineral thortveitite, which has been found in Madagascar (20 pct Sc2O3) and in Norway (35 pct Sc2O3). Scandium also occurs in small but distinct amounts in uranium and rare-earth ores; the recent larger scale processing of these materials has made some scandium available from these sources. As with other naturally-occurring monoisotopic elements (except Be), scandium contains an odd number of protons and an even number of neutrons. Scandium metal was first prepared by Fischer and coworkers1 in 1937 by electrolysis of scandium chloride in a molten eutectic mixture of lithium and potassium chlorides, using molten zinc as a cathode and collector of the scandium metal produced. The zinc was removed from the Zn-2 pct Sc alloy by vacuum distillation, leaving a product reported to be 94 to 98 pct Sc, with the main impurities being iron and silicon. They reported a melting point of 1400° C for this material. Scandium has also been prepared by the reduction of scandium chloride with potassium metal in a glass apparatus by Bommer and Hohmann in 1941,&apos; resulting in a mixture of metal and potassium chloride; these workers did not isolate the metal proper, but the X-ray diffraction of the slag-metal mixture showed it to be hexagonal with a = 3.30A, c = 5.45A. petru3, 4 and coworkers have recently reported the preparation of the metal in a compact form by the reduction of either ScF3 or ScC13 with calcium metal and subsequent distillation of the product. This process probably yielded a metal of high purity, but they list no chemical analysis nor do they list any of the properties of their product. Previous related work in this Laboratory has been concerned with the production of yttrium and the rare-earth metals and the determination of their physical properties. Because of its similarity to these metals, scandium is being included in this study. PREPARATION OF SCANDIUM METAL The preparation of yttrium and the rare-earth metals may be accomplished by reduction of their fluorides with calcium metal in tantalum crucibles.5 This process leads to the introduction of tantalum (up to 0.5 pct) as an impurity in the higher melting rare earths, but since the tantalum occurs as dendrites, uncombined with the rare-earth metals, its presence is not objectionable in some cases. The preparation of scandium metal in this manner, however, was found to yield a product containing 2 to 5 pct Ta. To obtain a purer product, the following two methods were developed for the reduction of scandium fluoride with calcium metal: i) a low-temperature process utilizing zinc to form a low

Jan 1, 1961

Discussion of the paper of E. G. Woodruff, presented at the Butte meeting, August, 1913, and printed in Bulletin No. 78, June, 1913, pp. 1001 to 1010. F. A. LINFORTH, Butte, Mont.:-I have not had an opportunity of reading this paper thoroughly, but I would like to call attention to the possible use of the contours on fault planes. It is obvious that if the contours of fault surfaces call be determined, we will be able to determine the axes of the hollows in the fault surface. It seems probable, and there are examples to point to the accuracy of, the assumption, that the axes of these hollows may be the direction of movements on the faults, and if that is true it will aid materially in locating faulted ore bodies or the shoots of ore on the opposite sides of faults. A few such contour maps of faults have been attempted on some of the faults of the Butte district, and those faults which are believed to have the nearly normal movement exhibit for the axes of these hollows a line nearly up and down in the plane of the fault, but in those cases where the throw is believed to bee nearly horizontal we find that the axes of the hollows are almost horizontal lines. In other words, the movements on faults, I believe, would be more nearly indicated by the larger grooves in the fault surfaces than by the small slickensides and minor hollows that are seen, so that contour maps might be valuable in geology in that way. C. W. GOODALE, Butte, Mont.:-I received a letter from Mr. Woodruff asking me to take part in the discussion of his paper, but I have not had time to give the paper any study. I can certainly add my opinion to that of all the engineers here that the topographic maps of the government are of great aid to the engineer. When I visit a new district, the first thing I do is to see if that district has been covered by the U. S. Geological Survey avid if topographic map has been issued. And I find that some of the younger engineers frequently come into my office to see if I have such maps. I know in some cases the reports made out by engineers contain copies of these topographic maps, or clippings from them. I am sure that. the topographic maps furnished by the government are of very great value to our engineers.

Jan 11, 1913

By Prince Lazarovich, Hrebelianovich

I WAS asked by the chairman of one of the Sessions on Employment Problems to talk about the viewpoint of the foreign workingman. I am not a workingman. I have never done what a work-hand might call an honest day&apos;s labor; that is, I have never been in a factory or manufacturing plant or in a mine, though in truth, hard work and I are well acquainted. I was a soldier, am an engineer, have long been actively interested in the most important waterway construction in the near East, have served politics and diplomacy, written books and lectured at universities. My knowledge of the foreign workingman in this country comes from the fact that my own compatriots here at various times came to me and appealed for advice and help, and last year I was asked by the employment manager of a corporation to undertake a welfare job at one of their plants. I went out, saw the plant, talked with the superintendent and outlined certain of my ideas which he personally heartily approved, but which did not find favor with those higher up. I approach the subject of the foreign workman&apos;s point of view with the understanding that the industrial employer&apos;s effort is for the maximum of efficiency. I am conversant with labor conditions abroad both in industry and agriculture. What I have learned of industrial conditions in America as they affect the foreign immigrant has been chiefly gathered from the cases referred to of foreign workmen who from time to time have come to me with their troubles. In the course of those investigations, in order to give whatever help or advice was possible, I have been impressed with the fact that the great United States industries evidently had- pot yet sufficiently recognized the value of studying the conditions of the workingman in the lands of his origin across the seas. A careful study of that which could be called the moral element in connection with its foreign labor would give industry a knowledge of the man&apos;s reason for coming, what&apos; grievances he brings with him, his hopes for a future, and the peculiar character of his capacities. The employer would thereby be enabled to meet the man, to be helpful to him, to aid him and at the same time promote industrial efficiency, inasmuch as a workman who believes that he is being dealt with humanly and squarely is contented and satisfied and will give willingly, and even with pride, the best that is in him; justice and a fair deal is all the man wants.

Jan 4, 1918

By Prince Lazarovich Hrebilianovich

I was asked by the chairman of one of the Sessions on Employment Problems to talk about the viewpoint of the foreign workingman. I am not a workingman. I have never done what a work-hand might call an honest day&apos;s labor; that is, I have never been in a factory or manufacturing plant or in a mine, though in truth, hard work and I are well acquainted. I was a soldier, am an engineer, have long been actively interested in the most important waterway construction in the near East, have served politics and diplomacy, written books and lectured at universities. My knowledge of the foreign workingman in this country comes from the fact that my own compatriots here at various times came to me and appealed for advice and help, and last year I was asked by the employment manager of a corporation to undertake a welfare job at one of their plants. I went out, saw the plant, talked with the superintendent and outlined certain of my ideas which he personally heartily approved, but which did not find favor with those higher up. I approach the subject of the foreign workman&apos;s point of view with the understanding that the industrial employer&apos;s effort is for the maximum of efficiency. I am conversant with labor conditions abroad both in industry and agriculture. What I have learned of industrial conditions in America as they affect the foreign immigrant has been chiefly gathered from the cases referred to of foreign workmen who from time to time have come to me with their troubles. In the course of those investigations, in order to give whatever help or advice was possible, I have been impressed with the fact that the great United States industries evidently had not yet sufficiently recognized the value of studying the conditions of the workingman in the lands of his origin across the seas. A careful study of that which could be called the moral element in connection with its foreign labor would give industry a knowledge of the man&apos;s reason for coming, what grievances he brings with him, his hopes for a future, and the peculiar character of his capacities. The employer would thereby be enabled to meet the man, to be helpful to him, to aid him and at the same time promote industrial efficiency, inasmuch as a workman who believes that he is being dealt with humanly and squarely is contented and satisfied and will give willingly, and even with pride, the best that is in him; justice and a &apos;air deal is all the man wants.

Jan 1, 1918

By Richard S. McCaffery, Morrison B. Yung

While assaying some copper carbonate ore from the Frazer claims, Similakameen, B. C., I noticed that on parting the gold button a deep orange solution was formed. The button gave off pink bands in the nitric acid, which became deep orange at a short distance from it; and as it traveled over the surface of the porcelain dish, it left a deep orange track behind. As the button brightened in the cupel, it appeared to have a bronze color; but I have since found that when amarillium is in large excess of the gold, the button is a very dark gray. The button parted easily. To the orange solution I added a salt (NaCl) solution, shook in a silver testbottle, and filtered. With H2S I obtained a precipitate, which I supposed due to platinum. However, on further tests, it did

Jan 1, 1903

C. A. Stetefeldt, San Francisco, Cal. (communication to the Secretary): In view of Mr. Louis&apos;s statement that the balance and weights employed in his experiment were &apos;(by no means first-rate," the results can scarcely be entitled to weight. And if a slight variation in specific gravity were to be accepted as proof of the existence of allotropic modifications, we should be obliged to conclude that every metal existed in such modifications. When the observed specific gravity of an alloy (as is often, and perhaps generally, the rase) differs from the calculated one, it seems more reasonable to explain the difference (apart from errors of determination) by assuming that actual chemical combination takes place between some atoms of the metals. MR. Louis (communication to the Secretary): In reply to the criticisms with which Mr. Stetefeldt has favored me, I beg to point out to him that, in the first place, I do not myself attach very much weight to the results I have obtained. I merely claim to have pointed out that amorphous gold obtained from dissolving up the alloy with silver has a higher specific gravity than common gold—a result corroborated by the quoted results of Rose. At any rate, it is easy to repeat my observations, and I hope this may be done by men who have better opportunities than myself for this investigation. Surely it is worthy of attention from assayers at the mints. I am not prepared to say that I should regard slight variations in specific gravity as absolute proof of allotropism, but I do consider

Jan 1, 1894