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By C. W. Mueller, P. H. Robinson

A technique was developed for depositing single -crystal films of silicon on single-crystal sapphire substrates via the pyrolytic decomposition of SiH4/H2 mixtures. Electron diffraction and X-ray Laue reflection examinations of these films revealed single-crystal patterns. These films were characterized by measuring conductivity type, thickness, resistivity, and Hall mobility. Chemical etching, dislocation staining, and electron-microscopy examination have indicated the presence of low-angle grain boundaries and microtwinning in the silicon films. The role of the sapphire substrate with respect to its quality, orientation, surface finish, and thermal and chemical treatment was investigated. Hall mobility as a function of sapphire orientation was measured. A mobility equal to 88 pct of bulk silicon mobility was attained. Insulated-gate field-effect transistors which have a transconductance of 4000 pmho at 6 ma were fabricated using these films. THE technology of the fabrication of microelectronic circuits with active and passive components directly on a single wafer of semiconductor material has attained a high degree of perfection during the last few years. One inherent difficulty with the single-wafer approach has been undesirable coupling between components arising from the common base material. Several techniques have been developed for minimizing this coupling and obtaining good electrical isolation between components; however, these result in extra capacitance being added to the circuit. The extraneous capacitance of the connecting leads, resistors, and capacitors degrade circuit performance and limit the high-frequency operation of these circuits. Recently there has been considerable interestl-3 in the deposition of silicon films upon insulating substrates. The use of silicon as the semiconductor allows the subsequent utilization of the large amount of technology which has been developed for silicon for the fabrication of good active components. A sapphire substrate supplies an excellent insulating material which at the same time gives a thermal-conductivity improvement of an order of magnitude over glass-type substrates. This paper will describe the results obtained for the deposition of single-crystal silicon layers upon single-crystal sapphire substrates as well as the characterization of these films. I) APPARATUS The 'system used for the growth of silicon films on sapphire substrates by means of the pyrolysis of SiH4/H2 mixtures is shown in Fig. 1. The all-quartz reaction chamber is water-cooled and includes a quartz optical-flat window for use in conjunction with a 5 kw, 2.5 Mc per sec constant-temperature controlled rf generator. The temperature sensor for the rf generator is a thermopile which is focused through the quartz optical flat onto the susceptor surface. With this system the rf generator will hold the temperature of the susceptor to about +0.3°C at 1200°C. The susceptor is supported on a quartz sled inclined to the gas flow to increase the uniformity of the deposition. The water jacket surrounding the reaction chamber is used to keep the quartz wall temperature low enough to limit the decomposition of the silane to the rf-heated susceptor which contains the sapphire substrates. This eliminates the reaction of silicon with the hot quartz to form SiO which deposits out on the apparatus walls, thus obscuring vision, and interferes with the optical measurements of the temperature as well as with the growth process itself. Provision is also made for "n"- and 'p"-type doping by using mixtures of either phosphine or diborane in hydrogen which are added to the silane during the growth process. The hydrogen used is the purest commercially available tank hydrogen further purified by use of a palladium diffuser. The susceptors which were used include 1) spectro-scopically pure graphite, 2) high-purity molybdenum, 3) high-resistivity silicon using a low-resistivity insert to facilitate coupling to the rf generator, 4) silicon carbide-coated graphite. The latter two susceptor materials produced silicon films on sapphire substrates with more reproducible resistivities. Prior to silicon deposition all connecting lines as well as the reaction chamber are thoroughly flushed with argon and then hydrogen. After the hydrogen flow is set, the growth temperature is adjusted to 11009 to 1150°C, and when thermal equilibrium is reached the silane flow is started. The flow rate of the hydrogen must be fast enough so that turbulent flow occurs in the size of reaction tube used, otherwise a streaked nonuniform silicon deposit occurs. After the deposition

Jan 1, 1967

By John Johnston

WHEN I was honored by being invited to give the Howe Memorial Lecture, I decided to read Howe's book, "The Metallography of Steel and Cast Iron," published in 1916-that is, about 25 years ago-in search of a text. I found the book written in fine, clear, attractive, yet precise style, as I expected, knowing that his father ¬Dr. Samuel Gridley Howe, his mother-Julia Ward Howe, and all of his four brothers and sisters had lived in a New England literary atmosphere and had written books. This leads me to suggest that many authors of metallurgical papers and books could well study Howe's writings with a view to the improvement of their own. I failed to find a specific text, but did find a subject, for in reading his book I was struck by the few instances in which time is considered explicitly as a factor in the phenomena examined, and by the fact that many of the hottest arguments would have been settled had time been taken properly into account. Indeed, Howe hardly mentions time except in a rather incidental way, as in a few references to lag; for instance: The lowering of temperature at which the transformation occurs by rapid cooling . . . is a phenomenon of undercooling or lag. It is in part explained by the fact that the transformation itself is a time-consuming reaction which, setting in during a rapid fall of temperature. is naturally protracted till the temperature has sunk far below that at which it is due. He does discuss, quite fully, the iron-carbon equilibrium diagram, as known at that time, introducing it by stating: As he is a reasonable man who is not deterred from using a hand truck for moving his trunk by the consideration that he has thus to move a trunk plus a truck, so am I reasonable in putting into your hands this useful, indeed indispensable, tool for mastering the ABC of iron metallurgy. Somewhat later, in introducing a discussion of the phase rule, which "it would be hardly proper to pass . . . by without an attempt to outline its meaning," for "a clear exposition of its applicability or jurisdiction is needed to restrain the half-initiated from misusing it and the uninitiated from being misled by these misuses," he writes-and I quote his statement because we cannot properly discuss the influence of time on a process until we know the state of equilibrium which would ultimately be reached by the system under consideration It is a most remarkable and valuable generalization, its conceptions help greatly toward getting a broad outlook on metallography, but its misconception has brought out a flood of obscuring writings. It tells us about the constitution towards which alloys tend, that which they reach when equilibrium is complete, when all tendencies have corrected themselves and have been complied with completely. Its application, in absence of true equilibrium, is like determining density with a telescope or even with a tuning fork; it is like the mad tea party at which the butter put into the works "f the watch was the best butter. If the reader learns no more than to beware of attempts to decipher the conditions of inequilibrium by a law which touches only the conditions of exact

Jan 1, 1942

By J. G. McCullough

The paper is a general description of the U.S. lead and zinc industries as they are now compared to ten years ago and the effect of recent world-wide developments. Topics of interest concerning lead are the present and potential growth of the lead-acid battery business, the potential hazards of having one outlet for a major proportion of production, the expanding U.S. secondary lead production, the hardships of stringent hygiene and environmental regulations and the future supply and demand outlook. The present poor condition of the U.S. zinc industry caused by an oversupply of zinc metal - mostly in Europe - is discussed and also the shifting markets influenced by the automotive programs to reduce the weight of cars and the continuing high mine production due to the mixture of metals contained in the massive sulphide deposits which contain a major portion of the zinc metal reserves. This is all tempered by technical advances in die casting and the emphasis on the protecting of steel with zinc to prolong its useful life. New U.S. mine and smelter production facilities will be restrained due to lower cost foreign zinc from better grade ore deposits and the insistence by Governments for refining capacity to be constructed in the country that the ore is mined.

Jan 1, 1977

By A. G. Guy

Thermodynamic activity rather than chemical composition is basic to the analysis of diffusion. This is the essential conclusion reached by Darken1-3 and by Birchenall and Mehl.4 If so, it is reasonable to expect that diffusion calculations should be carried out using activities. This paper will illustrate a method of employing activities in analyzing interstitial diffusion. For interstitial diffusion (of carbon in iron and probably generally) the diffusion of the solvent atoms, volume changes, and other such complexities not explicitly provided for in the usual diffusion equations cause a negligible error of the order of 1 pct. Therefore it is relatively easy to test the validity of an analysis based on activities in the instance of interstitial diffusion. The mathematical treatment of the more complex substitutional diffusion could be simplified once the adequacy of the activity method had been established for substitutional diffusion. Thus the present work has the purpose not only of providing a superior analysis of interstitial diffusion but also of indicating a possible approach to the more important question of an adequate treatment of substitutional diffusion. Development of the Diffusion Equation Although activities are convenient quantities to determine experimentally, they are derived from the more fundamental fugacities.9 Possible confusion in using activities can be avoided by basing equations involving their use on the relationship, dP = -D1d/ax dt [I] where, dP = the number of grams of solute crossing one cm2 in the time dt sec. D, = the diffusion constant for use with fugacities; it is assumed to be constant at a given temperature, and has units of secs. f = the fugacity of the solute in the solid solution; the units are those of pressure, dynes per cm2. x = the distance in cm. Eq 1 can be considered to be the basic form of the first Fick Law for one-dimensional diffusion. In order to convert Eq 1 into an equation involving activities, a choice of a standard or reference fugacity, f°, must be made: then. a = f [2] where a is the activity corresponding to the fugacity f. However, the value of a is also determined by the relation, a = a\c [3] where a is the activity coefficient and c is the concentration. For a given value of a (such as a = 1) it is evident that the units used for expressing concentration will affect the numerical value of a corresponding to a given amount of carbon dissolved in y-iron. Since weight per cent concentration is so widely used, this unit will be adopted as the standard in this paper. When the value off given by Eq 2 is substituted in Eq 1, the first Fick Law becomes, dP= -D,f°dl [4] Since D,f° is constant (at a given temperature), the second form of Fick's Law can be obtained in the usual manner, -dt D'f° dx [5] where c' is the concentration in g per cm3. In terms of weight per cent concentration, c, Eq 5 becomes, dc _ 100 d2a Tt = T /f w [6] where p is the density of the solid solution and will be assumed to be constant. In order to simplify Eq6, it is necessary to consider the standard state, f°. Standard states are chosen for convenience. There appears to be one especially convenient choice for the analysis of interstitial diffusion. If the activity coefficient, a, is set equal to unity at infinite dilution of the solute, 100 then — 100D1fl° is approximately equal P to the usual diffusion constant in dilute solutions. This is true since the activity, a, in Eq 6 can be replaced by the concentration, c, with little error in an infinitely dilute solution.* Here f1° is the standard fugacity necessary to achieve this standard state. It is proposed that a diffusion constant Da' be defined, Da1=100/pD1f1° [7] where A is the metal whose diffusion is * The second derivative of a is equal to the second derivative of c in dilute solution only if -da/dr- is. zero. Although theory does not require this condition, in the systems C in Fe, and Zn in Cu, dc is in fact found to be essentially zero.

Jan 1, 1950

By G. C. Hancock

The operating plant of The Broken Hill Associated Smelters Pty. Ltd. is situated at Port Pirie in South Australia and it treats to finality the whole output of lead concentrates from the mines of The Zinc Corporation Ltd., North Broken Hill Ltd., and aroken Hill South Ltd. at Broken Hill, New South Wales. Lead bearing ores from other sources are also purchased for treatment and lead scrap and residues are treated on a toll charge basis. The present output of the plant is approximately 200000 tonnes of refined lead per annum and there is a substantial production of by-products including refined silver, gold, cadmium, antimonial lead alloys, copper matte and sulphuric acid. Recently the Company commenced the production of zinc by slag fuming and electrolysis from a six million ton dump of lead blast furnace slag, which has been accumulating at Port Pirie for over fifty years. The slag fuming plant contains two furnaces of conventional design, but features a high degree of pre-heat for the blast air and this is obtained by the use of all-metal recuperators. The raw zinc oxide fume produced by the plant is roasted in a rotary kiln prior to treatment in the leaching and electrolysis sections, which follow conventional practice for nigh current density plants. Present output is approximately 36000 tonnes of electrolytic zinc per annum.

Jan 1, 1970

By Henry S. Washington

I. INTRODUCTION. DURING the last twenty years or so the chemical investigation of rocks has made great advances, and it is now generally recognized that a knowledge of the chemical composition is as essential as that of the texture or mineral composition-if not more so-for the proper classification of rocks and study of their origin and relationships. Rock-analyses have vastly increased in number and, what is of greater importance, in quality. New and improved methods permit of greater accuracy than was possible in the early days, and the list of chemical constituents frequently determined has risen from the seven or eight of the greater part of the nineteenth century, to twenty or more. Indeed, rock-analyses with determinations of so many constituents ire now commonly made by the chemists of the United States and Australia, while in Germany, Great Britain, France, and Italy the rarer constituents are determined more frequently-than formerly. As a consequence of this modern, accurate work, it has been discovered that some elements which were formerly supposed to be rare are of wide-spread occurrence and are often present in considerable amount. The fact is further being developed that the elements tend to show certain relations of occurrence or abundance in connection with each other. This is a fact which is applicable to the rarer elements, and which also finds a broad geological and petrological expression in the recognition of petrographic provinces. We are beginning to obtain some definite, though as yet rudimentary, knowledge of the distribution of the elements among igneous rocks. Some of the results along these lines obtained by study of the vast accumulation of analytical data now available are well known to petrologists, while others do not seem to be so gener-

Jan 1, 1913

By E. A. Holbrook

RESEARCH, primarily, is finding out the truth. Research applied to engineering opens the door to new principles and processes, the application of. which benefits mankind in a material way. The engineer believes that investigation instituted with the primary view of making the results directly applicable to the industries is the highest type of research. Coal is essentially the basis of modern industrial civilization; therefore, any, considerable research pertaining to coal must link itself to the industry by, practical application of the results of the research. In other words, all investigational work connected in any way with coal leads to conclusions that permit a better understanding of the origin, nature of occurrence, composition, better and safer mining, more careful preparation, or greater efficiency in utilization of coal. Modern engineering research has been fostered essentially by universities and in the laboratories of institutions of learning. Coal problems that lend themselves to solution in the laboratories have been first attacked and are perhaps the farthest toward solution. For example, a great amount of research work has been carried out with the various phases of chemistry connected with coal. On the other hand, the equally important problems connected with methods of mining have received but little attention, primarily because their solution involves the continued use of a great and expensive laboratory, which is none other than the mine itself. As many of the problems already solved have had chemistry as their background, so many of the problems unsolved have physics as their background; there are also unsolved problems that deal in- coal economics. Even psychology must be called upon in future coal-mining research as a basis for solving those great problems that deal with human relationships. In general, considerable advance has been made in coal research dealing with chemistry, not so much progress has been made with problems having physics and engineering as a background, while there is a tremendous range of untouched problems that deal essentially with business and psychology.

Jan 9, 1919

By George A. Roberts, Arthur H. Grobe

Tensile, hardness and density properties are presented for a new 18-8 stainless steel powder for the —50, —100, and —140 mesh cuts and also for a prepared blend containing 62 pct —325 mesh powder. The data were obtained for sintering temperatures of 2100° to 2350°F and for compacting pressures of 30 to 50 tons per sq in. A NEED has existed for a stainless steel powder of uniform composition from particle to particle, which could be readily molded and sintered, and which would yield moderate to high strength and ductility when processed into parts by standard powder metallurgy techniques. The literature reveals that previously available powders have been lacking in one or several of these desirable characteristics. Originally attempts to produce stainless steel powder by blending and diffusing elemental metal powders were unsuccessfu1.l A truly alloyed stainless steel powder reported by Dale in 1947 yielded reasonable mechanical properties but required an exceptionally high sintering temperature of 2400°F in pure dry hydrogen.' A later development reported in 1950 by Stern provided a stainless type powder of excellent molding properties' but this powder likewise required sintering at temperatures over 2350 °F and did not yield properties as high as those previously reported. The powder was not truly alloyed prior to sintering. A prealloyed stainless steel powder has been developed that is readily moldable at 30 to 50 tons per sq in., can be sintered at low temperatures (2100" to 2300°F), and which yields compacts with both high strength and ductility. The powder is prepared by the liquid disintegration method," direct from molten metal. Early attempts to make 18 pct Cr, 8 pct Ni stainless steel powder by this method did not produce a usable powder for pressing and sintering because of a preponderance of spherical particles with relatively high, surface oxide content. It was learned that silicon additions to iron alloys, powdered by this process, gave bright powder of low-oxide content and such additions were made to 18-8 stainless with similar results. An attendant change in particle shape occurred reducing the number of spheroids materially. The optimum composition which has been studied and is reported here contains approximately 2.5 pct Si. Silicon additions to stainless steel of the 18-8 type improve the resistance to high-temperature oxidation and promote the formation of ferrite. Corrosion resistance is, however, controlled by chromium content and even though ferrite may exist the corrosion resistance is not generally impaired.4 Experimental Procedure A detailed study of the 18-8, 2.5 pct Si powder has been made in accordance with the following outline: 1. Four blends a. — 50 mesh b. —100 mesh

Jan 1, 1952

By T. K. Redden

Protective coatings based on the formation of a surface coating of nickel aluminide (NiAl) were applied to the nickel-base superalloys IN 100, SEL 15, and U-700. Coated specimens were exposed to an oxidizing environment at temperatures between 1600 and 2200 F for times up to 1000 hr. The oxidation resistance and stability of the coating were evaluated by weight gain measurements, metallographic examination, and X-ray diffraction study of surface oxides and coating. The composition of the coating and diffusion zone was determined by electron microprobe traverse of samples before and after high-temperature exposure. Intermediate phases formed in the coating and diffusion zone were identified by X-ray diffraction in situ and after electrolytic extraction. The outer coating was found to consist of the inter-metallic compound, NiAl, while the diffusion zone contained MC, M23C6 or M6C carbides, and a phase in a matrix of NiAl + Nidl. Oxidation resulted in formation of an A1203 n'ch scale containing some Tz02. Depletion of aluminum during oxidation resulted in degradation of the outer coating to Ni3Al and the nickel alloy matrix. Diffusion of aluminum into the base metal was found to be slight and did not influence coating life significantly. The o formed in the diffusion zone during coating decomposed during elevated-temperature exposure to form stable carbide phases characteristic of the base metal. Diffusion zone phase changes were found to have no effect on the life of the aluminide coating in the oxidizing envzron?nent. THE oxidation resistance of many high-strength nickel-base superalloys is inadequate for extended exposure at temperatures above about 1600°F. In addition, some applications for these materials require that they be exposed to environments containing sulfur compounds and sodium salts which can cause surface attalk known as sulfidation or hot corrosion. In order to provide the necessary corrosion resistance to the high-strength alloys, protective coatings based on an aluminizing process have been developed. These processes, usually based on a pack cementation technique, result in the formation of a NiAl-rich outer coating layer either during the coating process or by a subsequent diffusion treatment. The performance of the aluminide coatings is affected by interactions between the coating layer and the base metal both during the coating process and during subsequent exposure at elevated temperatures. Knowledge of these interactions is required to guide the development of coatings capable of longer life and improved reliability. Goward et al.' recently reported the metallurgical factors which influence coating per- formance on MAR-M200. The present work is concerned with correlating the interactions and performance of coating compositions on several representative materials. EXPERIMENTAL PROCEDURES Materials. Three cast nickel-base superalloys which are used for turbine buckets in air-breathing engines were studied: IN 100, U-700, and SEL 15. Their chemical compositions are given in Table I. The alloys were vacuum-induction-melted and cast to slabs approximately 0.3 in. thick from which rectangular specimens 0.25 by 0.5 by 1 in. were machined. Coating Procedures. The machined specimens were coated by CODEP processes which were developed at the author's laboratory. These are based on pack cementation in various media to deposit either aluminum or aluminum in combination with titanium. The coating process which deposits only aluminum is designated CODEP-C, while the CODEP-D process deposits titanium in combination with aluminum. The CODEP-D process was applied only to IN 100. Both CODEP processes are applied at 1950" or 2000°F for 4 hr without need for a subsequent diffusion treatment. An outer coating about 1 mil in thickness is produced by these processes. Test Procedures. Coated specimens were exposed to static oxidation for periods ranging from 24 to 1000 hr at temperatures of 1600" to 2200°F. Terminal weight gain measurements and visual examination were used to evaluate oxidation resistance. including oxide spalling and coating failure. Both as-coated and exposed specimens of each alloy were studied by metallographic examination, electron microprobe analysis (EMA), and X-ray diffraction analysis either of the exposed surfaces or of phases extracted from the coating and diffusion zone. RESULTS As-Coated Condition. The microstructures of as-coated conditions were generally similar, irrespective of base materials or the particular coating process. They are typified by IN 100 coated by CODEP-D as shown in Fig. 1. The predominately single-phase outer layer, area A, Fig. 1, was identified by X-ray diffraction as the intermetallic compound NiA1. The NiAl zone extended inward to the original base metal interface. The diffusion zone, area B, Fig. 1, included carbide phases, a lamellar phase oriented perpendicular to the base metal surface, and a matrix phase consisting of a mixture of NiAl and Ni3Al. The phases in the diffusion zone were electrolytically extracted using a 10 pct HCl in methanol solution at approximately 1.3 amp per sq cm. The extracted phases were found to be M6C, MC, or M=C6 carbides and o as shown in Table I1 for each of the alloys. The d spacings from a typical diffraction pattern are

Jan 1, 1969

By R. F. Hehemann, S. T. Zegler

The w phase in zirconium alloys containing more than G pct Nb can form in a difjUsionless manner during quenching or with composition change during aging at temperatures below 550°C. The latter treatment establishes a metastable equilibrium between an w phase containing 5 pct Nb and a ß phase containing 45 pct Nb. The superconducting transition temperat~ire of quenched Z?-10 pct Nb and Zr-15 pct Nb alloys is increased by aging at 375°C and both alloys exhibit the same Tc after prolonged aging. The superconducting transition both in the quenched and in the aged alloys is relatively sharp (occurring ovev a temperature range of <0.5°K), and is interpreted in terms of the microstructure that characterizes the ß-w) mixture and proximity effects postulated for thin-film superconductors. At elevated temperatures alloys of the transition elements from groups 4 to 6 in the periodic table exhibit wide ranges of mutual solubility in the bcc structure. Except for compositions that are high in a group 4 element? the bcc structure can be retained at room temperature by quenching and several systematic studies of the influence of composition on superconductivity in bcc alloys have been reported.&apos;&apos;2 The high-temperature bcc form (ß) of the group 4 elements—titanium, zirconium, hafnium—is not retained upon quenching but instead transforms marten-sitically to the hcp structure (a). The Ms temperature can be lowered by alloying the group 4 metals with a solute from a higher group and with a critical amount of solute the martensitic transformation can be suppressed. The 3 phase, however, is not retained without modification. Rather, a metastable phase, w (in particular in titanium- and zirconium-base alloys), occurs over a fairly wide range of compositions above that required for suppression of the martensitic transformation.3,4 As in the formation of a, the transformation of ß to w occurs in a diffusionless manner during quenching and the temperature for its initiation (ws) is lowered by increasing solute content. The ws temperature can be well below room temperature and reversibility of the transformation allows w that forms on cooling to low temperatures to disappear again when the sample is returned to room temperature.5 In Zr-Nb alloys the w phase can also be formed during aging at temperatures below 550°c.5 In this treatment, a metastable equilibrium is established between a niobium-rich ß phase and a zirconium-rich w phase. The present study of Zr-Nb alloys was undertaken to examine the influence of microstructure: as controlled by composition and heat treatment, on the superconducting transition temperature, Tc. MATERIALS AND PROCEDURE The alloys were prepared from zirconium crystal bar that was spectrochemically pure except for 30 ppm of Al, 40 ppm of Cu, 100 ppm of Fe, and 1 ppm of each B and Pb. The niobium used was 99.5+ pct pure containing according to the suppliers&apos; (Stauffer Chemical Co.) analysis a maximum of 50 ppmO, 60 ppm of N, 30 ppm of C, 5 ppm of H, 200 ppm of Ta, 50 ppm of Mo, and 15 ppm each of Fe, Co, and Ni. The alloys were prepared in the form of buttons weighing approximately 4 g by arc melting on a water-cooled copper hearth in an inert-gas atmosphere. All alloys were heat-treated in the ß-phase region for 3 days at 1000°C and water-quenched. For heat treatment, the specimens, 0.5 cm in diam by 1.0 cm long, were wrapped in zirconium foil and sealed in an inert-gas atmosphere inside quartz capsules. Quenching was done by breaking the capsules under water. Subsequent aging treatments of Zr-10 pct Nb and Zr-15 pct Nb alloys were done by placing the specimens in a lead bath at 375°C and quenching in chilled brine. The phases present in the quenched and aged alloys were identified by optical and X-ray metallography. X-ray powder patterns were taken at room temperature with a 114.6-mm-diam Debye-Scherrer camera and CuK-a radiation. Superconducting transition temperatures were determined from magnetic-permeability measurements6 in a 10 oe field. The superconducting transition temperature was determined from a plot of galvanometric deflection as a function of temperature by extrapolation of the linear portion of the curve to zero deflection. In Figs. 1 and 3 the arrows indicate the temperature range of the transitions. RESULTS AND DISCUSSION Superconductivity in Quenched Alloys. In Fig. 1 Tc for alloys quenched from 1000°C is plotted against nominal composition. Indicated also in Fig. 1 are results of metallographic studies. Alloys containing less than 5 pct Nb transform martensitically to a during quenching from 1000°C and Fig. 1 demonstrates that Tc increases significantly as the niobium concentration in a is increased. On the basis of the Bardeen-Cooper-Schreiffer theory of superconductivity7 it seems most likely that this increase in Tc results from an increase in the density of electronic states as zirconium is alloyed with niobium. This increased density of states has been revealed clearly in low-temperature specific-heat measurements.8 The martensitic transformation to a is suppressed when the alloy content exceeds 5 pct Nb. In the range from approximately 6 to 30 pct Nb, quenched alloys consist of a mixture of B and w phases and the amount

Jan 1, 1967

By C. A. Heiland

A. INTRODUCTION (C. A. HEILAND) I. PRINCIPLES OF TEMPERATURE COMPENSATION IN MAGNETIC INSTRUMENTS The principle underlying the majority of magnetic intensity variom-eters is a comparison of the force to be measured with another force of known magnitude. The known force may be (a) of a magnetic nature, such as magnetic fields produced by magnets or coils, or (b) of a mechan-ical nature, such as (1) the elastic forces of wires, or (2) the force of gravity, such as employed in bifilar magnetometers and magnetic balances. In instruments of such type, usually a magnetic system is employed, free to move about either a horizontal or vertical axis, on some sort of a suspension. If the earth&apos;s magnetic field alone were present, such a system would adjust itself into the direction of the field or that of its components. Owing to the simultaneous action of the comparison force, however, the magnetic needle assumes a position that differs from the direction of the magnetic force; for all such instruments, the angle of deflection a is given by tan a = F/X, where F is the known and X the unknown earth magnetic force component. In other words, the magnetic system merely serves as an "indicator" for the position of balance of the two forces. Considering the matter from this point of view, it is not immediately obvious why the temperature of such a magnetic system should modify the results. In magnetic instruments, we may distinguish two different effects of temperature: (1) a magnetic effect and (2) a mechanical effect. The first is due to the fact that the magnetic moment of a magnet drops with an increase in temperature. This drop is characterized by the temperature coefficient of the magnetic moment µ (see equation 1). The second effect is due to the change in the .torsion of suspension wires with temperature or to the expansion of lever arms of masses acting on magnetic balances.

Jan 1, 1932

By J. W. Gwinn

The underground haulage system in the lead-silver mine of the Bunker Hill & Sullivan Co., situated at Kellogg, Idaho, is the most extensive in the Cæur d&apos;Alene district, comprising about 35,000 ft. of tunnels, drifts, and cross-cuts where locomotive haulage is in use. The main working adit, known as the Kellogg tunnel, or No. 9 level, is approximately 10,000 ft. in length from the portal to the main working shaft and extends beyond that about 4,500 ft. in each of two directions. On this level all the ore from the Bunker Hill & Sullivan, the Sierra Nevada Consolidated, and the Caledonia Mining Co.—an average of 44,600 tons per month—is hauled to the mills, located a short distance from the portal. Electric haulage by the trolley-type locomotive is used on this level throughout. Below this level, at intervals of 200 ft. vertically, are five other working levels (Nos. 10, 11,12,13, and 14); and the total haulage distance on these, where electric locomotives are used, is approximately 16,000 ft. No. 13 level has but recently been opened up and is not working to capacity; while the main cross-cut on No. 14 has just been started, and has no need of power haulage. Of the four levels equipped with electric haulage, Nos. 11, 12, and 13 have storage-battery locomotives, and No. 10 still retains the trolley type by reason of the small and decreasing tonnage produced. Electrification - Electric power is supplied to the mine by two systems. The first, the 500-volt direct-current trolley, was installed in 1897 when the Kellogg tunnel was started, and was extended as the tunnel advanced, being used for the first trainload of ore on Nov. 17, 1902, since which time it has been in continuous service. The current for the line is transmitted on a No. 00 copper wire as far as the shaft, and on No. 0 wire throughout the remaining length of the Kellogg tunnel; and until the installation of the storage-battery locomotives it was used in practically all the cross-cuts and drifts on each level below No. 9.

Jan 1, 1915

By Robert H. Richards

The object of this paper is to enlarge the field of settling velocities treated by me in my former papers, Close Sizing Before Jigging, and Sorting Before Sizing.&apos; There seemed need of work both on coarser and on finer sizes. Messrs. A. Sidney Warren and M. L. Nagel undertook the investigation for the coarser sizes, from 12.85 mm. down to 2.05 mm. diameter. Their work, because of the closer spacing and because of the increased number of observations and consequent stronger averages, called for a revision of the former work. Messrs. G. A. Barnaby and Ralph Hayden undertook this part of the work, from 2.49 mm. down to 0.28 mm., which is near the limit of sifting. Their work covers the ground much more minutely and comprehensively than the former papers. There remained to be covered the portion of the field too fine for investigation with the sieves. This part, covering the range of grains from 0.48 to 0.03 mm., was undertaken by Mr. E. S. Bardwell. For it he used the elutriation method. 11. The First, or Coarsest, Section of the Field. The first desideratum in this investigation was a series of sieves for sizing the sands preparatory to making the tests. It became necessary, therefore, to decide on a sieve-scale for this purpose. A sieve-scale is a series of sieves in which the dimensions of the holes of the successive members form a series increasing by a definite ratio. There are three natural sieve-scales: 1, progressing by doubling the width of the hole for each suc-

Jan 1, 1908

By H. R. Wuthrich

The Metallgesellschaft AG decided in late 1965 to build an Electrolytic Zinc Plant at Datteln (W. Germany). Lurgi-Chemie was entrusted with the engineering and erection of the entire plant. Ground was broken in February 1967 and the operation was started on August 1st, 1968. The new Electrolytic Zinc Plant was designed to produce a minimum of 100,000 metric tons of special high grade zinc and 200,000 metric tons of sulphuric acid. Concentrates from Meggen (W. Germany) and mainly Timmins (Canada) are roasted in two turbulent layer roasters. The sulfur dioxide containing gases are converted in a "Bayer double catalysis unit" to sulfuric acid. The calcine is leached batch wise, the leach residue separated from the pregnant solution by counter-current thickeners and drum filters. For maintaining the sulfate balance a modified jarosite leach is being used. After a two step purification the neutral solution is mixed with spent electrolyte and cooled in unpacked atmospheric cooling towers. Three electrical circuits are supplying the power to the tankhouse, each rated at 30,000 amperes. With a maximum current density of 750 amperes per square meter and a stripping cycle of 24 hours, an average current efficiency of 90 percent is obtained. Cathodes are melted in one induction furnace and cast into shapes, or alloyed with aluminum and copper for die-cast metal.

Jan 1, 1970

By Albert Sauveur

Floris Osmond, Honorary Member of the American Institute of Mining Engineers, born in Paris, March 10, 1849, died at Saint-Leu near that city, June 18, 1912. Taken suddenly ill with congestion of the brain while on his way from Paris to his home, he reached it in time to write on the typewriter his last wishes, one of which was that no biographical notice of his life should be published. Holding Osmond&apos;s memory sacred, as those who have known him will, is it our duty to conform with his desire ? Shall no mention be made in our Transactions of the beautiful life and great achievements of one of our most honored members? Is it not, on the contrary, incumbent upon us to disregard Osmond&apos;s instruction in this matter and to place on record our admiration for the nobility of his life, for his talents and for the importance of his work, that younger men may be inspired by it with a desire to be guided by worthy motives in the path of unselfish pursuits ? I cannot feel that in following this course I am disloyal to Osmond&apos;s memory and I am strengthened in this belief by the opinion of men of high honor whom I have consulted before undertaking the writing of this obituary notice. One of them, Professor Henry M. Howe, justifies my decision better than I could do it myself when he writes : " Let us look frankly at the matter. Here we have a most extraordinary life, a life of rare beauty and power of inspiration to the rest of mankind. In my opinion we should not deprive mankind of the stimulating influence of the example of M. Osmond simply because he shrank from publicity. Our young men see every day how greed and vulgar push succeed, and with what material rewards they are crowned. They see too rarely the more valuable crown which comes to self devotion. A permanent and public recognition of the beautiful qualities of Osmond&apos;s life cannot fail to appeal to the imagination of young men and to help to deflect them toward leading a noble rather than a sordid life. Therefore I feel that the Revue de Métallurgie and other bodies owe it to the public to give prominence to his career by means of biographical notices."

Jan 1, 1914

By AIME AIME

SOMETIMES family backgrounds have a deep, if not direct, influence on a man&apos;s lifework. Dean Callen&apos;s paternal grandfather came from Wales and was a mine official in the Pennsylvania anthracite field: his maternal grandfather was a retail coal dealer. His father and uncle began their careers a. breaker boys but later completed their educational work and ended up in the professions. With that background, and with the slate region ( Pen Argyl, Pa.. July 1;. 1888) as his birthplace it is not strange that "Cope" Callen became a teacher of mining engineering. Graduating from Lehigh with an E.M. in 1909, lie taught there for two years while working for his master&apos;s degree. In 1911 he returned to teaching, going to the University of Illinois as instructor in mining engineering. In 1917, he was called to West Virginia University as head of the department of mining engineering and director of mining extension. The extension work was about dead. bus a new staff was built and the six-weeks&apos; short course in coal mining was revamped into an attractive and efficient course which has grown in popularity with the years. Callen&apos;s work attracted the attention of the Federal Board for Vocational Education and in 1919 he was invited to serve that board as special agent for mining, taking a six-months&apos; leave front the University.

Jan 1, 1944

By D. R. Wieland, A. N. Barron, A. R. Hendrickson

A definite relationship has been found between the reactivity of flowing hydrochloric acid and its shear rate in a carbonate fracture. Both flow velocity and fracture width affect the acid reaction rate. Laboratory studies were conducted on acid reactivity at different flow velocities through horizontal-linear fractures, using 15 per cent hydrochloric acid at 80&apos; F and approximately 1,100 psi. Fracture width varied from 0.02 to 0.20 in. These data provide a new basis from which the spending time and penetration of the acid can be estimated. Equations were derived expressing the relationship between injection rate, fracture width, acid concentration, time and fracture height, for linear and radial fracture systems. Because the penetration of the acid before spending is closely related to the extent of productivity increase resulting from an acidizing treatment, these data provide a valuable insight into some of the controlling factors that must be taken into consideration during treatment preplanning. INTRODUCTION Acidizing of carbonate reservoirs to improve production characteristics has been widely practiced since 1932. Originally, it was assumed that the acid uniformly penetrated natural formation pores and flow channels, enlarging them and thereby increasing their flow capacity. Little consideration was given to the reaction rate of the acid, or how far it would penetrate away from the wellbore into the formation, before spending. It has been shown recently&apos; that, unless fractures are present in the rock, very little penetration is attained before spending, and the benefits of the acidizing treatment are largely confined to the immediate vicinity of the well-bore. Therefore, acid treatments may be classified into two categories: (1) matrix acidizing, in which the acid flows through multiple: formation pores; and (2) fracture acidizing, in which the bulk of the acid travels through fractures in the rock, whether natural or induced. When acidizing treatments are conducted at pressures of sufficient magnitude to open and extend such fractures, it is often desirable to inject a propping agent to hold the fracture open after the treating pressure has been released, thus providing a highly conductive flow channel through the rock. In some cases where acid attack produces surface irregularities, the resulting flow passages can be sufficient to provide high conductivity without use of a propping agent. During injection, the acid dissolves the carbonate rock with which it comes in contact until it is spent. Deeper penetration of the spent acid into the formation produces no appreciable benefit (if no propping agent is used) because the unetched fracture faces will rejoin when treating pressures are released and the fracture will "heal", with negligible resultant conductivity. The spending time of the acid thus becomes important in determining how far from the wellbore the improved-conductivity zone extends. The spending time of acid after injection into carbonate rock depends on the rate at which the acid reacts with the rock. This in turn is controlled by a number of factors, as previously reported. 2-4 These include temperature, pressure, acid concentration, rock composition, injection rate and the area-volume relationship between the acid solution volume and the surface area of the formation flow channels through which it penetrates. Thus, in matrix acidizing, where an extremely large area is exposed to the acid, spending is rapid. In contrast, spending time is prolonged in open fractures, where the area-volume ratio is much lower. Thus, greatest penetration of the acid before spending will be achieved in acid-fracturing treatments where fractures are held open by hydraulic pressure. Perkins and Kern5 have presented equations for fracture-width determinations which, for hard formations such as limestone or dolomite, indicate that high injection rates and viscous fluids are required to create wide fractures. Increasing the injection rate will, in itself, produce faster reaction rates. Because this type of reaction can be considered to be first-order diffusion-controlled, &apos;-&apos; the rate of movement of fluid past the rock surface affects the thickness of the diffusion layer, in turn affecting the reaction rate. Staudt, et al,10 report the results of tests in which a rotating marble cylinder was immersed in acid, and the weight loss at different speeds determined. Such test conditions, however, are not truly indicative of the situation in a formation during an acid-fracturing treatment. This paper reports reaction-rate data obtained under

By Charles White Merrill

Mankind&apos;s progress is measured in minerals. Man&apos;s emergence from prehistory is marked by passage through a Stone Age and a Bronze Age and into the present era, sometimes called the Iron Age or the Age of Metals. With the evolution of civilization and the development of a modem industrial economy, minerals become more and more important. Structures, roads, and machines are built largely of minerals; the energy to heat the structures and to drive the machines is mostly mineral; agricultural fertility is maintained by mineral fertilizers and water; and military strength is provided by fortresses, armaments, and munitions, largely of mineral origin. Thus in the material world, in the productivity of the economy, access to minerals has paramount importance. Every evidence indicates increasing dependence on minerals in the modem economy, particularly on the mineral fuels as energy sources to provide the power base for advancing industrialization. Both the total and the per capita consumption of almost every mineral is increasing in the industrialized nations. Moreover, nations with predominantly agrarian economies call themselves underdeveloped and universally strive to industrialize. Most mineral consumption trends in the more advanced economies have been greatly exceeding population growth-which itself has been advancing at an accelerating rate--and sometimes have surpassed the growth in real income. Some minerals have only recently been adopted or grown to importance in use. Titanium as a metal appeared as a commercial product only in 1948, and even coal seriously displaced wood as a source of heat less than two centuries ago. On the other hand, minerals have always played an important role in construction. The prehistoric megaliths that form the dolmens of Salisbury Plain are stone; the pyramids are andesite faced with limestone; and many other ancient structures are built of mineral materials. In modem times the whole course of architecture has been redirected by new building materials, mostly mineral. Most conspicuous is the sky-

Jan 1, 1959

R. F. McELVENNY.- Mr. Oldright has just given me a letter to read to you, which I think it may be of interest. It is headed, "Silver Meeting Dinner". The letter is as follows: "To Members of the A. I. M. & M E.: The annual business meeting and election of officers will take place at the University Club, Wednesday, May 28th, 1930 at 7 p.m., at the Silver Meeting Dinner. The Nominating. Committee for next year&apos;s officers have proposed the following names: Chairman, Robert Wallace; Vice-Chairman, G. W. Crane; secretary, C. T. Van Winkle, Other nominations can be made at the meeting. Utah being the leading silver producer of the United States, constructive suggestions regarding the silver situation will be made at this meeting which are new and of general interest to the members. The speak¬ers will be followed by a Round Table discussion of the silver situation and proposed remedies. Speakers will be - W. M. Ferry, President of the Silver Producers&apos; Association, &apos;Recent developments in the Silver Question&apos;.. Senator Frank J. Cannon, &apos;The Cannon Plan&apos;. George W. Snyder, &apos;The Manufacture of Sterling Silver.&apos; Discussion by J. J. Beason, G. W. Crane, J. 0. Elton, J. W. Wade and others. Members of the Conference on Copper Reverberatory Smelting are invited to be present. Chairman J. A. Norden will preside. C. T. Van Winkle, Secretary. Dinner will be $1.50 per plate." The next subject is "Boilers: Proper construction of, so as to secure best utilization of heat from gases, and facility in removing dust and clinker with minimum losses in operation." Who is particularly interested in that subject? The type of boilers is practically a standard practice now. I do not know of anybody that is using the tandem system now. No one is building a plant with a tandem system in it.

Jan 1, 1930

By A. A. Venghiattis

A rational approach to the selection of the appropriate perforator to use in each specific zone of an oil well is presented. The criteria presently in use for this choice bear little resemblance with actual down-hole condilions. These environmental conditions affect the elastic properties of rocks. One of these elastic properties, acoustic velocity, is suggested as the leading parameter to adopt for the choice of a perforator because, being currently measured in the natural location of the formation, it takes into account all of the effects of compaction, saturation, temperature, etc., which are overlooked in the laboratory. Equations and curves in relation with this suggestion are given to allow the prediction of the depth of perforation of bullets and shaped charges when an acoustic log has been run in the zone to be perforated. INTRODUCTION When an oil company has to decide on the perforator to choose for a completion job, I wonder if it is really understood that, to date, there is no rational way of selecting the right perforator on the basis of what it will do down-hole. This situation stems from the fact that the many varieties of existing perforators, bullets or shaped charges, are promoted on the basis of their performance in the laboratory, but very little is said on how this performance will be affected by subsurface conditions such as the combination of high overburden pressure and high temperature, for example. The purpose of this paper is to show the limitations of the existing ways of evaluating the performance of perforators, to show that performances obtained in laboratories cannot be extended to down-hole conditions because the elastic properties of rocks are affected by these conditions and, finally, to suggest and justify the use of the acoustic velocity of rocks, as the parameter to utilize for the anticipation of the performance of a perforator in true down-hole environment. EVALUATING THE PERFORMANCE OF A PERFORATOR It is natural, of course, to judge the performance of a perforator from the size of the hole it makes in a predetermined target. Considering that the ultimate target for an oilwell perforator is the oil-bearing formation preceded in most cases by a layer of cement and by the wall of a steel casing, the difficulties begin with the choice of an adequate experimental target material. For obvious reasons of convenience, the first choice that came to the mind of perforator designers was mild steel. This is a reasonable choice for the comparison of two perforators in first approximation. Mild steel is commercially available in a rather consistent state and quality, and is comparatively inexpensive. The trouble with mild steel is that it represents a yardstick very much contracted; minute variations in depth of penetration or hole diameter and shape may be significant though difficult to measure. The penetration of projectiles in steel being a function of the Brinell hardness of the steel (Gabeaud, O&apos;Neill, Grun-wood, Poboril, et al), it is often difficult to decide whether to attribute a small difference in penetration to a variation on the target hardness or to an actual variation on the efficiency of the projectile. Another target material which has been widely used for testing the efficiency of bullets or shaped charges in an effort to represent a formation—a mineral target as opposed to an all-steel target—is cement cast in steel containers. This type of target, although offering a larger scale for measuring penetrations, proved so unreliable because of its poor repeatability that it had to be abandoned by most designers. The drawbacks of these target materials, and particularly their complete lack of similarity with an oil-bearing formation, became so evident that a more realistic target arrangement was sought until a tacit agreement was reached between customers and designers of oilwell perforators on a testing target of the type shown on Fig. 1. This became almost a necessity about seven years ago because of the introduction of a new parameter in the evaluation of the efficiency of a perforator, the well flow index (WFI). The WFI is the ratio (under predetermined and constant conditions of ambiance, pressure and temperature) of the permeability to a ceitain grade of kerosene of the target core (usually Berea sandstone) after verforation. to its vermeabilitv before perforation. The value of this index ;or the present state if the perforation technique varies from 0 to 2.5, the good perforators presently available rating somewhere around 2.0 and the poor ones around 0.8, There is no doubt that, to date, the WFI type of test is by far the most significant one for comparing perforators. It is obvious that a demonstration of a perforator