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By Sam F. Carter

FOR some time melters and metallurgists have recognized the fact that steels may be made to identical compositions as ordinarily analyzed, but with considerable variations in physical properties. Good melting practice signifies a combination of furnace operations that will produce steel with consistently good physical properties after proper consideration of cost, production efficiency, and chemical control. In acid practice, these operations may be classified fundamentally as: (I) the oxidizing boil, (2) recarburization and deoxidation, (3) slag adjustment, and (4) final deoxidation. These operations affect the properties of the steel through variations in the minute quantities of several microscopic, submicroscopic, and dissolved constituents, which are out of reach of ordinary analyses but are very influential upon the crystallographic slippage and the molecular cohesion of the structure. One of these constituents is the FeO left in solution in the steel. Herty has shown that steels high in dissolved FeO have decreased ductility and impact and increased hardness and electrical resistance. There is also much evidence that FeO in solution affects carbon solubility and diffusion, and consequently abnormality and carburizing behavior.

Jan 1, 1947

By Charles Prasky, Robert K. Zahl, John C. Nigro

Bench scale and pilot plant research was conducted using dolomitic (CaO - MgO) lime as the basic additive in the preparation of self-fluxed pellets from a typical magnetic taconite concentrate (5.5% SiO2). The specific objective of this investigation was to ascertain the viability of the magnesia lime pellets in high temperature oxidizing and reducing atmospheres. Pellet basicity and induration temperature were major parameters affecting fired pellet quality; temperatures ranging from 1200° to 1250°C appeared to be the most favorable for production of self-fluxed pellets with basicities (B) above 1.0. Comparison of the mechanical and metallurgical properties of regular (acid) and self-fluxed pellets (B = 1.55) produced under similar conditions in a modified grate pelletizing machine showed that the selffluxed pellets were more resistant to abrasion and to high and low temperature reduction disintegration, an important consideration in commercial application. The +3 mesh Linder index increased from 68% (regular pellets) to over 90% (self-fluxed pellets). The reducibility and swelling indices of the self-fluxed pellets were found to be comparable to the regular pellets.

Jan 1, 1974

By William P. Blake

(Canal Zone Meeting, November, 1910.) A DEPOSIT of manganese-ore near Tucson, Ariz., merits notice by reason of the peculiar form in which it occurs, and as a striking. example of ore-deposition by vadose upward capillary flow of metal-bearing solutions with concentration at the surface of the country-rock. This deposit occurs at the northern end of the Coyote mountains, about 40 miles west of Tucson, upon the outcropping beds of porphyritic rock, which appear to be partly-metamorphosed strata of volcanic tufa, probably of late Secondary or of Tertiary age. The strata dip northward at a low angle, and present a series of basset-edges in parallel lines of outcrop, east and west, facing the south and extending over many acres. Successive groups of these outcrops, from 5 to 20 ft. in breadth, are coated with oxides of manganese in lustrous black films and crusts, shining in the sunlight like polished ebony, and covering the whole surface of the rock above the soil. Seen at a little distance, these croppings look like solid ledges of massive and pure ore; but closer inspection and a few blows of the hammer reveal their true nature as a superficial coating allied in origin to the blackened shining surface of rocks exposed in desert-regions, familiarly known as " desert paint" or "desert varnish,"' similar to the phenomena described by me in a former paper, but much thicker and heavier. * By reason of the death of the distinguished author, this communication, probably his last communication to technical literature, is published without revision of the proofs by him. A term first given y G. K. Gilbert. See Rocks, Rock-Weathering, and Soil; by George P. Merrill, p. 256 (New York, 1897). Superficial Blackening and Discoloration of Rocks, Especially in Desert Regions, Trans., xxxv., 371 (1905).

Sep 1, 1910

By Thomas E. Garnar

Zirconium and hafnium are curious elements because they are almost always found together in nature. Zirconium was discovered by Klaproth in 1789 and isolated 35 years later by Berzelius. Because hafnium's chemical properties are so close to those of zirconium, it was not discovered until 1923 when Coster and Von-Heresey detected it using x-ray spectrographic analysis. These elements occur most commonly in nature as the mineral zircon (ZrSiO4) and less commonly as the oxide baddeleyite (ZrO2). They also are found as a variety of other silicates. Zircon was identified as a component in alluvial and beach sands in 1895, but it was not produced in any quantity until 20 years later. Zircon is always a coproduct from TiO2 mining and processing. During World War I it was produced as a coproduct of beach sand mining for titanium minerals just south of Jacksonville Beach, FL, and was patented as a refractory. It was not until the 1930s when Zircon Rutile, Ltd. began mining at Byron Bay on the east coast of Australia that zircon was first used as a foundry sand. Later in the 1940s, NL Industries, Humphreys Gold Corp., and E. I. du Pont de Nemours & Co., Inc. began production of zircon sands from fossil beaches in northeast and northcentral Florida. Baddeleyite first became available as a commercial product in 1916, but never in the quantity of zircon. Zircon holds a unique position as an industrial mineral because it is used for both its physical and chemical properties as well as an ore of zirconium and hafnium metals. Australia is the major zircon producer followed by South Africa and the US. Zircon is also produced in India, Sierra Leone, Sri Lanka, Malaysia, China, Thailand, and Brazil. Undeveloped heavy mineral beach sand reserves containing zircon are known to occur in Egypt, Malawi, Senegal, and Tanzania. Locations are shown in Fig. 1. Mineralogy Zirconium and hafnium are always present together in naturally occurring compounds. Most commonly they form as the silicate sometimes containing iron, calcium, sodium, manganese, and other elements. Less commonly they are found as oxides in combination with titanium, thorium, calcium, and iron. Zircon is the most common form. It is extremely resistant to weathering, therefore, often it is present in ancient beach sands and placer deposits. Although resistant to alteration from external sources, it is vulnerable to internal alteration as the result of thorium and uranium substituting for zirconium either in the zircon lattice or in solid solution. Alteration to the metamict state takes place as radioactive emanations from these elements disorder the crystal lattice, accompanied by hydration, reduction in specific gravity, and changes in color. The mineralogy of zircon and baddeleyite and variation of physical and chemical properties are shown in Table 1. The effects of zircon's internal alteration and darkened color can be corrected by heating to 1000°C for 30 min or so. A certain time-temperature relationship makes it possible for decolorization and reordering of the crystal lattice to take place when heating at higher temperatures for shorter periods or at lower temperatures for longer periods. After heating, x-ray diffraction patterns are sharper, the grains may be harder, and except for particles of malacon, the grains will be white or colorless in the absence of grain surface coatings. The color change is only temporary and the particles slowly darken with time. Zircon fluoresces light yellow in shortwave ultraviolet light. If exposed to ultraviolet light for extended periods of time, white (calcined) zircon turns purple. With time the induced color begins to fade and eventually disappears (e.g., calcined Florida zircon exposed to ultraviolet light for 24 hr still retains faint, but discernible, purple color after six months).

Jan 1, 1983

By B. C. H. Steele, C. B. Alcock

In choosing solid oxide electrolytes for use in the measurement of thermodynamic quantities at high temperatures, the two most important criteria are the values of the partial ionic and electronic conduc tizities. Measurements of these conducticities have been made for some Group IVA oxides and solid solutions of these oxides with CaO, Y2O3, and La2O3. The total conductivities as a function of temperature. oxygen partial pressure, and composition were determined, as well as the electromotive forces of cells in which the oxygen partial Pressures of the electrodes were between 10-7 and 10-29 atm at 1000°C. Additional factors that influence the experimental arrangements, such as the operating temperature, the appropviate cell atmosphere, and electrode kinetics, are also discussed. IT has long been recognized that galvanic cells incorporating solid electrolytes can possess many advantages for the measurement of high-temperature thermodynamic data. Unfortunately, the electrical-transport properties have only been established for a few solid electrolytes, although attempts have been made, and are still being made, to use such materials as porcelain' and magnesia.' Kuikkola and Wagner have discussed3 and demonstrated4 various applications of solid electrolytes, and, in particular, their work stimulated the electrochemical measurement of oxygen activities using cells incorporating the solid oxide electrolyte, Zr0.85Ca0.15O1.85 The excellent characteristics of this oxide electrolyte have been confirmed by the investigations of Kingery et al.5 (oxygen ion diffusion), Carter and Rhodes6 (zirconium and calcium ion diffusion), and Weissbart and Ruka7 (electronic transference number). However the observations of Peters and Mobius,8 later confirmed by Schmalzried,9 indicated that the electronic component of zirconia-based electrolytes could become significant at low oxygen chemical potentials. Under these conditions, thoria-based electrolytes have obvious advantages arising from their superior thermodynamic stability. It was known that certain thoria solid solutions possessed defect fluorite structures containing anionic vacancies (cf. Zro.85Cao.l50O1. 85), although data on their electrical properties were conflicting. Kiukkola and wagner4 concluded that thoria-based electrolytes exhibited appreciable electronic conductivity, whereas Peters and Mobius8 mentioned that the electronic conductivity only became important at high oxygen partial pressures, but gave no further details. In addition, both Kiukkola and wagner4 and Peters and Mann'" had determined the oxygen chemical potentials associated with the Fe-FeO, Co-COO, Ni-NiO, and Cu-Cu2O equilibria, and it was not known whether discrepancies in their results could be attributed to the different cell design, or the thoria-based electrolyte used by Peters and Mann. These uncertainties have been resolved during the present investigation into the measurement of low oxygen chemical potentials, and transport properties of the relevant oxide electrolytes are presented and discussed. Other experimental difficulties associated with low oxygen chemical potential measurements are also described, with particular reference to the Nb-O system. 1. THEORETICAL CONSIDERATIONS Oxide systems of potential use as solid electrolytes possess a large energy gap between the valence and conduction bands. Little is known about the defects present in these wide-gap metal oxides as a function of impurity content and deviations from stoichiom-etry, or the mechanisms by which electronic charges move in these solids. For these materials it is convenient to represent the measured conductivity as the the sum of three terms: where a, is the conductivity due to positive hole conduction (p type), and oe is the electronic conductivity due to electron conduction (n type). U there is a large concentration of ionic vacancies fixed by composition then the ionic contribution will not be a function of oxygen pressure. Although the possibility of a pressure-independent electronic component also cannot be ignored, it is likely that such a term would only become significant at very high temperatures, and in general the positive hole conduction will increase with increasing oxygen pressure, and the electron conduction will increase with decreasing oxygen pressure. It follows that the total conductivity is related to oxygen partial pressure as follows:

Jan 1, 1965

By Kazutami Imai

Effects of heavy metal ions on the growth and the activities of iron and sulfur oxidation of Thiobacillus ferrooxidans were investigated. Mercuric, silver, and stannous ions inhibited both of the growth and the iron- oxidizing enzyme system of the bacterium. On the other hand, uranyl ion inhibited the growth, but it gave almost no effect on the iron-oxidizing enzyme system. The inhibitory effect of uranyl sulfate on the growth of the bacterium is intensified on lowering the cultivating ' temperature from 28 ºC to 7 ºC. In the concentration of 10-3M, cadmium and copper ions inhibited colloidal sulfur-oxidizing activity of the cells 69 and 52 %, respectively, though they did not inhibit the iron-oxidizing activity at all in the concentration. On the contrary, stannous chloride did not givr any effect on the sulfur-oxidizing activity of the cells, though it inhibited the iron-oxidizing activity 55 % in the concentration of 10-3M. Several differences were observed among the cytochrome systems of cell-free extracts of the cells grown on iron and on sulfur.

Jan 1, 1976

By G. D. Rieck, M. M. P. Janssen

Chemical diffusion coefficients and heats of activation for diffusion in the NizAh fy), NiAl (6), and Ni3A1 (E) intermetallic phases and the solid solution of aluminum in nickel (( phase) were calculated from layer growth experiments. No finite diffusion coefficient for the NiAl3 ((3) inter metallic phase could be calculated. The values of the diffusion coefficients are dependent both on the method of calculation and the type of diffusion couple. The heat of activation for diffusion in the y phase was found to be 47 kcal per mole in the temperature range oj 428" to 610°C. Heats of activation of 41, 12, and 48 kcal per mole were found for diffusion in the 6, E, and ( phases, respectively , in the temperature range of 655" to 1000°C. Experiments with markers in the diffusion zone demonstrate a very pronounced Kirkendall effect. It appears that only aluminum atoms take an active part in the diffusion process during the formation of the 0 and y phases at temperatures of about 600°C. During the formation of the 6, E, and < phases at higher temperatures only nickel atoms are moving. It is suggested that the great stability of the intermetallic compounds in the Ni-A1 system governs the Kirkendall effect. SOME factors controlling layer growth during inter-diffusion in the Ni-A1 system (phase diagram, see Fig. 1) were studied by Castleman and Seig1e.l&apos;~ They found the NiA1, ((3) and NiAl3 (y) intermetallic compounds to appear in the diffusion zone of Ni-A1 couples at annealing temperatures of 400" to 625°C; the NiAl (6) and Ni3A1 (E) intermetallic compounds appeared in y-Ni couples at annealing temperatures of 800" to 1050°C. These authors carefully examined metallographically Ni-A1 couples after 340 hr annealing at 600°C. Besides the (3 and y phases they found very thin layers of the 6 and E phases. ~n~erman~ and Castleman and Froot4 observed a much more rapid growth of the 5 and E phases at 600°C in Ni-A1 couples in case a crack was present at the /3-A1 interface. Numerous layer thickness measurements carried out by Castleman and Seigle on the y phase prove that the layer growth of this phase obeys the parabolic law after a certain transient period. From this they concluded that the layer growth of the y phase is controlled by volume diffusion. The growth of the 13, 6, and E phases appeared to be volume-diffusion-controlled also. The authors estimated that at 600°C and at atmospheric pressure Dp was 1.8 x lo-"ll sq cm per sec, D, 9.1 x 10" ™ sq cm per sec, Qp 27 kcal per mole, and Qy 31 kcal per mole. The present work was carried out to obtain more quantitative data about the kinetics of growth of the phases of the Ni-A1 system and the reactions that occur during the formation of these phases. Because in this system the diffusion process results in the formation of several distinct intermetallic compounds, the current term reaction diffusion is used in the title of this paper. In order to obtain layers of the fl phase compound of uniform thickness, a new technique for preparing diffusion couples was developed. The kinetics of growth of the y phase in 6-Al, E-Al, and Ni-A1 diffusion couples was studied at different temperatures. The kinetics of growth of the 6, c, and ( phases in Ni-y, Ni-6, and Ni-c diffusion couples was also studied at different temperatures. The calculation of the diffusion coefficients Dp and Dy by Castleman and Seigle are critically considered in this paper; by means of a revised method of calculation more reliable val-ues of , and Dg were found. These values are in good agreement with the values of the diffusion coefficients obtained by the method of Boltzmann-Matano. From the temperature dependence of the diffusion coefficients the heats of activation for diffusion were calculated by means of an Arrhenius-type equation. The investigation of the Kirkendall effect has been used to obtain information about the ratio of the intrinsic diffusion coefficients of the separate atoms5 and the mechanism of diffusion. Moreover porosity as a result of a distinct Kirkendall effect would be of practical importance in connection with the bonding of diffusion coatings. The analyses of the diffusion couples were carried out by metallographic methods. The values of the concentrations at the phase boundaries and the concentration profile in each of the phases, which are needed for the calculation of diffusion coefficients, were obtained by electron-pro be X-ray microanalysis. EXPERIMENTAL PROCEDURE A) Materials for Diffusion Couples. The intermetallic compounds 6 (50 at. pct Ni) and E (74 at. pct Ni) were prepared from the pure metals by high-frequency induction melting in argon atmosphere. Use was made of aluminum wire (99.99 wt pct Al) and nickel sheet (99.95 wt pct Ni). The 6 and E phase melts and the nickel shiet (thickness 0.1 and 0.5 mm) used for preparing diffusion couples were annealed for 64 hr at 1200°~ for homogenization and grain coarsening (final crystal size 1 to 3 mm). composition and homogeneity of the intermetallic compounds were checked by mi-crohardness measurements and X-ray diffraction. From the 6 and E phase melts discs of 0.5 mm thickness were prepared by means of a water-cooled rotat-

Jan 1, 1968

By E. Gybbon Spilsbury

(Pittsburg meeting, March, 1910.) THE recovery of gold and silver from their ores by means of the cyanide process has been so successful in the last few years that any radical improvement would seem impossible; yet the appliance to which I wish to call attention in this paper is really a radical departure from the methods now in general use. The most modern and approved of these, known as the all-sliming method, depends for its success on the grinding of the. ore so fine that practically 90 per cent. of it will pass through a 200-mesh screen. The slimes thus produced are then agitated and aerated in tanks of various types. The main object of this treatment is to insure such a thorough admixture of the pulp and solution that every particle of the ore is surrounded by a volume of solution sufficient to insure the dissolving of the whole of the gold- and silver-content. In addition, in order to expedite the action of the cyanide, and to oxidize such elements as would, if left in their active state, become cyanicides, air is blown in under pressure. In the Pachuca tank, this air is the active and sole means of agitation. The chief objections to all the methods off agitation used heretofore are the expense of operating and maintaining the mechanical devices for keeping the pulp in suspension, and the length of time required to obtain a fairly complete extraction. of the values. These objections are inherent to any method of agitation effecting a circulation of the pulp and the solution together, by giving the whole mass a circular movement, as in the low-tank system, or a vertical circulation, as in the Pachuca-tank system. In both methods, the particles of ore are kept traveling in the same direction as the solution, and with very little difference of speed; so that, while the whole mass is in

May 1, 1910

By Robert F. Mehl

EXTENSION of physical and chemical methods of research in the study of metallic behavior continues rapidly, particularly in the correlation of behavior with crystal structure, and in the analysis of elastic and plastic properties. The growth of the science of metals during 1933 calls for special comment; the need for special reviews and for textbooks and monographs is now acute, as might he supposed from the number of references appended to this article, a list which is much abbreviated.

Jan 1, 1934

By K. Tangri, M. Chaturvedi

The addition of 0.5 wt pct Cu to Zr-2.5 Cb alloy increases the as -quenched hardness of the hexagonal martensitic a&apos; phase, produced by water-quenching bccß-Zr phase, by about 35 pct. This strengthening has been attributed to the solid -solution hardening of the matrix. On aging ternary martensite, a&apos; phase reverts to equilibrium a and Zr2Cu and ß-Cb precipitate out, mainly at the twin and grain boundaries, causing a secondary hardening of the matrix. COLD-worked Zircaloy-2 pressure tubes have been in use in power reactors for a considerable period of time. The search for a better material led to the development of Zr-2.5 wt pct Cb alloy which in the quench-aged condition develops 50 pct more strength than that of cold-worked Zircaloy-2, however, its corrosion resistance in water and steam in the temperature range of 316" to 400°C, in absence of neutron flux, is inferior to that of zircaloy-2.&apos; Work carried out by Ells et al.1 and Dalgaard2 has shown that the corrosion properties of Zr-2.5 wt pct Cb alloy can be considerably improved by the ternary addition of 0.5 wt pct Cu. This paper is concerned with the effect of 0.5 wt pct Cu on the formation of martensitic a and its aging characteristics in a Zr-2.5 wt pct Cb alloy. MATERIALS AND EXPERIMENTAL TECHNIQUES Zr-2.5 Cb-0.5 Cu (referred to as the ternary alloy) and Zr-2.5 Cb (referred to as the binary alloy) alloys, supplied by the Chalk River Nuclear Laboratories of the AECL were used. The detailed chemical analysis is given in Table I. Cold rolling and swagging with frequent intermediate anneal of 1000°C were used for the initial fabrication of the alloys. All the heat treatments were carried out after the specimens were wrapped in zirconium foils and encapsulated in silica tubes under a vacuum of 5 x 10-6 mm of Hg. For optical metallography and hardness measurements specimens were mechanically and then chemically polished in a 45 pct HNOj, 45 pct HzO, and 10 pct HF solution. Hardness was measured on a Vickers hardness tester using a 10-kg load. For each specimen at least fifteen indentations were made in order to obtain a representative value. The phase identification and structural analysis were carried out using X-rays and electron diffraction techniques. Wires of 1.5 mm diam reduced to 0.12 mm diam by chemical etching were used for making Debye-Scherrer powder patterns using Cu Ka radiation in a 114.6 mm diam camera. Carbon extraction replicas were prepared by etching the specimens, after depositing a layer of carbon on the metallographic specimen, in one part HF and thirty parts ethyl alcohol. Thin films were prepared by electropolishing heat-treated 3/4 by 1/2 by 0.005 in. thick strips using a modified Bollman-Window technique. The 10 pct perchloric acid-90 pct methyl alcohol bath was kept at -50°C and polishing was done at 5 to 10 V. The thinned specimens were washed in ethyl alcohol at -30º to -40°C and dried between filter papers. Replicas and thin films were examined in a Phillips 300 G electron microscope. For resistivity measurements thin strip specimens 0.02 by 0.3 by 10.0 cm long were used. The potential leads were spot welded to the specimens in order to maintain a fixed length for the initial and the final resistivity measurements. The resistivity was measured by a Kelvin bridge in a temperature controlled room. The temperature was maintained at 72º ±1°F and the accuracy of the resistivity measurements was 0.03 µa-cm. RESULTS As-Quenched Structures. In order to produce a homogeneous matrix to study the precipitation reaction the solution-treatments of both the alloys were carried out in the -field region. From the Zr-Cb phase diagram due to Lundin and cox3 ß/a + ß phase boundary for Zr-2.5 wt pct Cb alloy is 820°C. Ells et al.1 have reported this boundary for Zr-2.5 Cb alloy containing 1100 ppm 0 to be at 920°C. Also, the addition of 0.5 wt pct Cu reduces this temperature by 50°C. Therefore, the solution-treatments were carried out at 1000°C to ensure that the alloys were in ß-phase region. The soaking time was 1 hr and the specimens were water-quenched. The as-quenched hardness of the binary alloy was 245 Vpn whereas, that of the ternary alloy was 330 Vpn. The X-ray diffraction studies indicated that the as-quenched structure of both the alloys consists of martensitic hexagonal phase a&apos;, with a c/a ratio of 1.591, and some retained ß-Zr. The presence of a&apos; phase was further confirmed by thin film electron microscopy. Electron micrographs of typical ß-quenched structures of the ternary and the binary alloys are shown in Figs. 1 and 2, respectively. Fig. 3 shows the diffraction pattern from an area similar to that shown in Fig. 1. Although, the as-quenched hardness of the ternary alloy is about 35 pct greater than that of the binary alloy, the structure of both the alloys seems to be the same. The matrix of both alloys is heavily twinned and shows very few dislocations. Furthermore, there is no evidence of any precipitation taking place in either of the two specimens during quenching from the solution-treatment temperature. Aging Behavior of Martensitic a&apos;. The aging kinetics of the ternary alloy were followed by resistivity and hardness measurements. The as-quenched values

Jan 1, 1970

By D. L. Katz, M. J. Rzasa

The derivations of three methods of computing the static pressure gradients in natural gas wells have been presented to show the assumptions made. Charts were developed from which the pressure gradients may be read when the well-head pressure, the well fluid gravity, depth, and the average well temperature are given. A chart for estimating the well fluid gravity from the condensate content and separator gas gravity is included. The effect of the increased average well temperature after flow on the calculation of the static pressure gradient is discussed. Introduction Reservoir pressures have been calculated from well-head pressures for gas wells for many years. As the pressure measurements become more accurate, the need for a reliable calculation of the static pressure gradient often arises. This paper will develop the several methods for computing the pressure gradient in gas wells and make a comparison between them. The method of calculating static pressure gradients in common use is Eq. I (ref. I) or its counterpart which includes a factor for the deviation of the gas from the ideal gas law. P2 - P1 = P1(e0.0000347GX _ I) Eq. [I] in which P1 = pressure at well head, lb. per sq. in. abs. PP = pressure at bottom of well, Ib. per sq. in. abs. G = gas gravity X = depth of well, ft. An alternate method is to compute the average density of the gas in the well and multiply by the well depth in a manner similar to that used for liquid gradients. Derivation of Formulas A static pressure gradient is a special case of the general fluid-flow equation. Consider a pound of fluid flowing in a vertical column from point I to point 2, Fig. I. By an energy balance for fluid flowing from I to 2: U1 + P1V1 + u12/2g + X1 + q = U2 + P2V2+ u22/2g+X2 +W [2] in which U = internal energy, ft-lb. per lb. P = pressure, lb. per sq. ft. V = volume, cu. ft. per lb. u = average linear velocity, ft. per sec. X = height above datum, fl. q = heat absorbed by fluid, ft-Ib. pcr lb. W = work done by system, ft-lb. per lb. An energy balance on the fluid itself gives: U = ?TdS - ?PdV + etc. [3] in which T = temperature, deg- R- S = entropy, ft-lb. per deg. R. per lb.

Jan 1, 1945

By M. L. Hammond, G. M. Bowers

Silicon dioxide films have been prepared on silicon wafers by the oxidation of SiH, near 400°C. Results previously reported by Goldsmith and Kern7 have been qualitatively corrobovated using a system of different geometry, and significantly greater deposition rates have been achieved. The deposition rate is independent of thickness and nearly independent of the O2/SiH, ratio over a wide range; however, the rate is strongly temperature-dependent. The structure of the deposit depends upon the cleanliness of the substrate, and the electrical field strength of the deposited oxide depends upon the nature of the electrodes. MULTILEVEL interconnects in integrated circuits using aluminum metallization require an insulator that can be deposited at low temperature. Because the A1-Si eutectic is only 577°C, the maximum deposition temperature must be below about 500°C to prevent reaction of the aluminum with the silicon and with other materials in the integrated circuit. Many methods of depositing insulating films of SiO, and other dielectrics have been reported&apos;-6 but the technique described by Goldsmith and Kern7 offers the simplest method of preparing SiO, films. The technique involves the reaction of SiH, and 0, to form SiO, films in the 300" to 500°C temperature range. Previous work using this gas system has been reported8 and the initial development work at Philco Microelectronics was done at the East Coast R&D Laboratories. 9 This paper corroborates some of the results of Goldsmith and Kern,7 shows that much higher deposition rates can be obtained than previously reported, and presents some observations on the structure of deposited SiO, films. EXPERIMENTAL CONDITIONS Fig. 1 is a schematic drawing of the apparatus used in this study. It differs from that of Goldsmith and Kern in that 1) the gases are mixed before they enter the reaction chamber, 2) there is no fritted glass diffuser, and 3) the wafers are stationary during deposition. The control thermocouple was in a well located 0.06-in. from the substrate, and three gas supplies were used: 1 pct SiH4 in N 2, O 2, and N 2. Water vapor must be excluded from the plumbing to prevent the formation of colloidal SiO, and the SiH4 must be diluted with an inert gas because SiH4-0, mixtures are extremely flammable above about 4 pct SiH The wafer temperature was determined by attaching a thermocouple to a test wafer and the temperature was maintained to +5 C. The conditions used in this investigation are listed in Table I. The temperature range was chosen for compatibility with the A1-Si system. The volume ratio of 0, to SiH4 is the actual volume of 0, delivered to that of SiH4, taking into account the initial dilution of the SiH4. This ratio, which was used by Goldsmith and Kern,7 is a useful indicator of the experimental conditions. The active/inactive ratio is the ratio of the volume of active gases, SiH4 and O2, delivered to the volume of dilution gas. The active/inactive ratio is an important parameter to specify for deposition rate determinations since it determines the amounts of reactants that arrive at the sample per unit time. Fairly high dilution ratios were necessary to achieve uniform deposits of SiO,. Most of the process characterizations were performed on the polished (111) face of 3 to 5 ohm-cm, n-type silicon wafers which were 0.009 in. thick; but the data approximately apply to deposition of SiO, on thin films of aluminum. It is difficult to obtain accurate deposition rate data over aluminum films because of coarsening the aluminum surface during exposure to 300" to 400°C. The deposited SiO, film fol-

Jan 1, 1969

Abadilla, Quirico A., Geol.. Lago Pet. Corp Box 172 Maracaiho, Venezuela. IIAbbw. Robert Graham. The W. W. Sly Mfg. Co.Train Ave.. Cleveland. Ohio. Abbotf A. N., Mines Supt., Maznpil Copper Co.. Ltd..Conception del Oro, Zac., Mexico. Abbotf Clarence E, Mgr.. Mines & Quarries, Tenn. Coal. Iron & R. R. Co., 1242 Brown Marx Bldg., Birmingham, Ala. Abbott. Louis Benjamin. Chief Engr.. Consolidation Coal Co. ... .Elkhorn Div., Jenkins, Ky. Abeel, George 8.. Jr., Cons. Min. Engr...4612 West 17th St., Los Angeles, Cal. Abel. Albert E.. Asst. to Pres.. Valley Mould & Iron Corp..Hubbard, Ohio. Abel. Raymond L Asst. Prof., Dept. of Pet. Refin.. Univ. of Pittsburgh. .. .Pittsburgh. Pa. Abernathy. George Elmer. Prof. of Geol. & Min.. Kansas State Teachers College. Pittahurg. Kans. Abernethy, D. Carl, Jr. Min. Engr., Hudson Coal Co. .Scranton, Pa. Abw, Hirouhi. Min. & Met. Engr., Min. & Met. Dept., The Higher Technical School, Osaka, Japan. Aborn. Robert H.. Research Assoc.. Mass. Inst. of Tech..Cambridge, Mass. Abouchar. Bylvain Sley. Min. Engr. & Geol., c/o S. H. Sekaly, 13 Rue El Nimr, Cairo, Egypt. tAbozeid. Mahmood. Pet. Min. Engr., Marland Oil Co. of California, Subway Terminal Bldg., Los Angeles, Cal. Abraham. Arthur W.A. pt. 40, Barcelona. Anzoatmui, Venezuela. Abrahams. Alexander I.. Gen&apos;l Mgr., Racon Electrical Co.. ..... .Slough, London, England. tAbrahamuon, C. W., Min. Engr.. The Mond Nickel Co., Ltd.. ..... .Levack. Ont., Canada. Abstein, Henry T.. Engr. & Mgr.. Profile-Tamarack Mines Co.. ...... .Yellow Pine, Idaho. tAcker, E. WC.. Met.. ........ .I28 East Washington Lane. Germantuwn. Philadelphia, Pa. IlAckerman, D. E.. Research Engr.. Research Lab., International Nickel Co., Bayonne, N. J. tAckerman. Ernest R., Pres., Lawrence Portland Cement Co.. . .Plainfield, Union Co., N. J. Adachi. Jinzoo.A..d dress Wanted Adachi, Yuichi, Chief Engr.. Anzan Steel Works, South Manchuria RY. Co., Anzan, South Manchuria. China. (Via Dairen). Adair, Arthur C, Valuation Engr., Internal Revenue. Treasury Dept.. . .Washington, D. C. Adami. Arthur E., Prof. of Min. Engrg., Montana State School of Mines. Butte, Mont. Adami. Charles J.. Min. Engr., Gen&apos;l Mnr., St. Jos~ph Lead Co.. ....... .Bonne Terre, Mo. Adama, C. W., Pres. Adams Pacific Corp .I66 Montgomery St., San Francisco. Cal. Adams. Cuyler .Dee rwood, Minn. Adams, David T, 514 Wrigley Bldg.. Chicago, Ill. ADAMS, FRANK DAWSON, Logan Prof. of Geology and Dean, Faculty of Applied Science. McGiU Univ., Montreal. Que.. Canada. Adams. Gale L, Research Engr.. General Pet. Corp...Los Angeles. Cal. Adams. George I.. Prof. of Geol. & Mineralogy. Univ. of Alabama. .Tuscalmsa, Ala. Adams. H. H.. Cons. Gml..Room 415, W. T. Waggoner Bldg., Fort Worth. Tex. Adams, Henry, Cons. Min. Engr. . 934 Park Ave., Plainfield, N. J. Adame, Henry H. 285 Madison Ave., New York. N. Y. Adams. Henry Farnum. Engr.. Charge Experimental Work, Inspiration Concentrator. Inspiration Cons. Copper Co.. Box 364, Inspiration. Ariz. Adams, Huntington, Min. Engr, 149 Broadway, New York, N. Y. Adams. Leland D, V.P.. Leslie-California Salt Co., 166 Montgomery St.. San Francisco. Cal. Adams. Louie W.. Illinois Steel Co Gary, Ind. Adama, XL L. Min. Engr.. Old Ben Coal Corp., Mine 12.. Christopher. IU. Adams, Robert M. Robert M. Adam Co. .I201 Fidelity Bldg., Duluth, Minn. Adams. Sidney F.. Geol., Empire Zinc Co .Gilman, Colo. tAdams, Waldo Peck..P ittsfield, Pike Co.. Ill. Addams. Charles 1. Min. Engr.. Bo x 663. Phoenix, Ariz. Addicka, Lawrence. Cons. Enar..... .61 Maiden Lane. New York. N. Y. Addison, Herbert, V.P.. Big Horn Collieries Co ,412 Colorado Bldg., Denver, Colo. Adkemn. J. Carson. Min. Engr.. HY Grade Manganese Co., Inc..Woodstock, Va. Ady. Joseph Wesley. Jr.. Min. Enar., 314 Mining Exchange Blda., Colorado Springs, Colo. Affelder. William Lewis. Asst. to Pres., Hillman Coal & Coke Co. & Allied Companies. 2006 First National Bank Bldg.. Pittshurgh, Pa. Ameck, B. F.. Pres.. Universal Portland Cement Co. .. .210 South La Salle St., Chicago. Ill. Agabeg, Edgar C.. Cons. Min. Engr.. ..... .Evelyn Lodae. Asansol, E. I. R. Bengal, India. tAsar. William M.. Aest. Prof. of Geol.. Kirtland Hall, Yale Univ.. ... .New Haven, Conn. Agaeniz. Rodolphe L, Pres.. Calumet & Hecla Consolidated Copper Co. ...... .Boston, Mass. tAgens, William Holmes. District Mgr.. Traylor Engrg. & Mfg. Co., 362 I. W. Hellman Blda.. Los Aneeles. Cal.

Jan 1, 1928

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 AIME AIME

AS director of Battelle Memorial Institute and as Chairman of the important O.P.M. advisory committee on metals and minerals, Clyde E. Williams numbers his acquaintances in the mineral industries by the thousands and h because his principal hobby is liking human beings, most of his acquaintancs are also his friends. Clyde is one of the many outstanding metallurgist, in the United States who started as a chemist. After graduating from the University of Utah in 1915 he was successively chemist for U.S. Smelting Refining and Mining Co., and at the Bureau of Mines station at Ithaca, N.Y. He then got into, metallurgical work and in 1920 he was appointed superintendent of the Northwest Station of the Bureau of Mines at, Seattle. Subsequently he was assistant to H. Foster Bain in metallugical work for the

Jan 1, 1942

By K. E. Nelson

The effect of thorium and zinc variations on the strength and 100-hr creep characteristics of Mg-Th-Zn-Zr alloys was investigated. Optimum resistance to creep at 650° and 700°F are attainable within a certain range of thorium and zinc contents. This range does not conform to that which develops maximum tensile properties. RAPID advances have been made during the last few years in the development of magnesium alloys for elevated temperature applications demanding high resistance to creep. The beneficial effect of rare-earth metals on the creep resistance of magnesium alloys has been emphasized by a number of publications1-13 and such alloys are now in commercial production. The use of thorium as an alloying ingredient in magnesium was mentioned by McDonald and also in two Alien Property Custodian patent applications.10,17 The initial observation of Sauerwald that thorium contributes still higher creep resistance to magnesium than is attainable with rare-earth metals has recently been substantiated.&apos;" " In fact, it has been demonstrated that the useful temperature range of magnesium alloys is appreciably extended by the use of thorium. In all cases, it was observed that zirconium must be included in the alloys in order to render them fine grained and more readily castable. Several recent publications:2-27 indicate that a still further improvement in creep resistance and a further extension of the useful temperature range can be realized by the addition of zinc to alloys. The primary purpose of this paper is to present the results of a comprehensive study of the effect of zinc on the strength and creep characteristics of Mg-Th-Zr alloys. Compositions covering the range of thorium content from M to 6 pct and zinc content from 0 to 5 pct have been investigated. The creep characteristics at 650" and 700°F reported in this paper are based on results of tests of 100-hr duration. It is appreciated that creep tests of 100-hr duration might not yield adequate data for design purposes for parts with much longer expected life. However, for the purposes of the present discussion, it is felt that the combination of stresses and temperatures used in the 100-hr creep tests have yielded a clear representation of the compositional variation of creep resistance at the temperatures investigated. Creep tests of 1000-hr duration are now in progress on a few of the most promising alloys. Preparation and Testing of Alloys The alloys studied in this intensive investigation were prepared in 25 lb capacity mild steel crucibles. The thorium, zinc, and zirconium were alloyed and poured as described in earlier publications The thorium was introduced into the melt in the form of a Mg-Th hardener," the zinc added in the metallic form, and the zirconium alloyed in the form of the commercial hardener containing magnesium and 30 to 50 pct Zr.10, 26 Fluxing practices for melting and refining were the same as for magnesium-rare-earth metal-zirconium alloys. The melts were sampled for analytical determinations and poured into separately cast 1/2 in. diameter standard tensile bars. The test bars were given a precipitation treatment of 16 hr at 600°F in laboratory furnaces. It has been shown by other tests that a high temperature solution treatment followed by an aging treatment is unnecessary for the development of optimum properties in Mg-Th-Zn-Zr alloys. The selection of 600°F as the aging temperature was based on an attempt to achieve metallurgical stability without coalescence of the undissolved phases and the attendant loss in strength. The thorium, zinc, and zirconium contents of each melt were determined chemically. The zirconium contents are reported in two parts, "soluble" and "insoluble," referring, respectively, to the portions present in the alloy which are soluble and insoluble in dilute HCl acid. Distinction is being made between these two components of the zirconium content in the alloys because it has been found that only that portion of the zirconium content which is soluble in dilute inorganic acids affects the structure and properties of the alloys. The usual impurities consisting of copper, iron, manganese, and nickel were determined spectroscopically. The analysis for each melt is listed in Table I. A description of the methods of tension and creep testing has been detailed in earlier papers. The tests were performed with the cast skin re-

Jan 1, 1954

By D. M. S. Bhatia

The intimate association of iron formation and massive sulfide deposits has been documented by many investigators (McAllister, 1960; Hutchinson, 1972). In a classic example of such an association, four distinct facies (oxide, carbonate, silicate and sulfide) were identified in an Algoma-type iron formation occurring in Paleozoic rocks, but exhibiting physical features (banding) and chemical composition (SiO2 + A1203 + Fe2O3) typical of Precambrian iron formations. The geochemical variation of the iron formation was studied by analyzing 62 samples for Si, Al, Fe, P, S, and Cop. Following a model proposed by James (1954), the geochemical and mineralogical variation of the iron formation can be used as an excellent tool for the exploration of massive sulfide deposits.

Jan 1, 1982

By N. W. Lord

The process of molten-zone refining is analyzed for long ingots and many zone passages. Formulas are derived which give the resultant impurity distribution in terms of finite series. A comparison with the approximate procedure of Hamming is given. HE physical principles and applications of an extremely physicalprinciple efficient form of metallurgical refinement has been described by Pfann. The purpose of the present paper is to describe a method of analyzing exactly the particular program used which enables the segregation effect to be predicted for any number of molten-zone passages in a long ingot. The method is applied to the particular case of refinement of an ingot whose impurity initially is uniformly distributed throughout its length. A number of molten zones of equal length are passed through the ingot effecting a radical redistribution of impurity. Pfann has indicated an approximate method, due to R. W. Hamming, of calculating the resultant concentration after each successive zone pass for a particular value of the segregation constant defined in his paper. Here a solution will be presented in terms of the number of zone passes and the segregation constant. The expression, though cumbersome, is exact and susceptible to ordinary numerical computation procedures. The results of a similar computation using the procedure of Hamming are presented in a table together with the exact results of the present method. The discrepancy in terms of absolute concentrations is tabulated for the first eight zone-lengths. To establish the notation (which follows that of Pfann1 as closely as possible) and physical basis of the analytical equations, the physical model and principal assumptions may be reviewed. An alloy of two elements, where there is formed a continuous range of solid solutions, usually does not melt as a simple compound. Rather, a temperature is reached where the solid solution is in heterogeneous phase equilibrium with a liquid solution of different composition. The temperature dependence of these equilibrium compositions forms part of the phase diagram. For very small concentrations of a solute B in a solvent A, this usually takes the form of Fig. 1. Sometimes the solidus and liquidus slope upward. This corresponds to a segregation constant (defined below) which is greater than unity. The segregation constant is now defined as k = Cn(x)/CnI(x) [1] where C,,(x) is the impurity concentration in the solid ingot at distance x during the nth passing of a molten zone and Cnl (x) is the impurity concentration of the liquid zone from which the solid at dis- tance x is formed (see Fig. 4 of ref. 1.) C (x) remains the same after passage of the zone. The constant k may be either greater or less than unity in general. Purification in the former case is effected only in a finite ingot and in the portion that is melted last. For k less than unity purification is effected even in an infinite ingot. The method which follows gives, in the former case, the successive increases in impurity concentration and, in the latter case, the successive decreases in concentration. The general case of impurity redistribution will be considered first, and purification will be discussed later on. The analysis rests on the following assumption: The movement of the zone is too rapid to allow appreciable atomic rearrangement in the solid sections and too slow to disturb the uniform impurity distribution in the liquid zone characteristic of equilibrium. Hence, the composition in the solid at the left solidifying interface will be determined by Eq. 1 while the impurity concentration of the liquid zone will be uniform throughout its length. The reasoning which follows closely parallels that of Appendix 11 in Pfann&apos;s paper. It is reviewed here for the case of the nth zone pass in order to make clear the meaning of an operator essential to the present method. Fig. 4 of ref. 1 shows the movement of a molten zone of length 1 in an ingot of total length d. Each Cn(x) can be determined from the condition that the amount of solute added to the zone during an incremental advance, dx, is due to the melting in of a solid portion C(x)dx and the freezing out of kCnl(x), that is d I —r- CnL (x) dx = Cn-1 (x+l)- kCnL (x) dx or, in terms of Cn(x) d k k —— C,(x) +—c.(x) =— Cn-1 (x + l). [2] dx l l This, of course, is derived from the main assumption, the fact that 1 is constant, and that the total impurity content previously present up to x + 1 is constant . A correction has to be made for the region (d — nl) < x < d. This is due to the zone length changing during the passage of the solidifying interface beyond x = d — 1. Since the general solution would be too complicated otherwise, only the region 0 < x < d — nl is considered. The general solution of Eq. 2 is

Jan 1, 1954

By P. W. Bridgman

DURING the war, the Navy undertook the construction, under my direction, of an experimental gun embodying features designed to lessen the cost and time of production. These experiments were initiated after representations as to their, desirability had been offered by myself, by the Naval Consulting Board, and by the National Research Council. The first drawings were made in June, 1917, and the experiment was completed in November, 1918. For the sake of clearness it will pay to recapitulate briefly the fundamental idea of gun construction. It is well known that if a hollow cylinder is subjected to internal fluid pressure, the maximum stress occurs in the inside layers, the outer parts carrying much less than their due share of the stress. This inequality of stress is more pronounced the thicker the walls of the cylinder. If such a cylinder is pushed to the elastic limit, failure in elasticity will take place long before the outer layers have reached the limit of their capacity. Economical use of the material would demand, however, that all parts of the cylinder reach the limits of their capacity simultaneously. This may be brought about, at least in cylinders of not too great thickness, by producing in. the inner layers an initial compression, and in the outer layers an initial tension. The effect of internal pressure is at, first to relieve the compression of the inside layers, while increasing the tension of the outside layers. If the initial stresses are properly distributed, all parts of the cylinder will reach their elastic limits simultaneously, thus giving a cylinder of maximum strength for its weight. In gun construction as hitherto practiced, this initial distribution of stress is produced either by winding the inner tube with wire, a common English practice, or by shrinking hoops over the inner tube, which has been the standard American practice. Either process is long and expensive, particularly with the larger guns, 12- or 14-in., which require

Jan 2, 1920

By P. Chiotti, J. T. Mason

Ther?nal, X-ray, metallographic, and vapor pressure data were obtained to establish the phase diagram and standard free energy, enthalpy, and entropy of formation for the compounds in the Sw-Zn system. Four compounds, SmZn, SmZn2 , SmZn4.s, and SmZn8.5, melt congruently at 960°, 94Z°, 908°, and 940°C, respectively. The cornpounds SlnZns, Sm3Znll, and SnzZn7.3 undergo peritectic decomposition at 855", 870°, and 890C, respectively. Another compound of uncertain stoichiometry, SmZn11, undergoes peritectic decomposition at 760°C. Four entectics were observed with the following compositions in weight percent zinc and eutectic tenzperatures in degrees Centigrade: 12 pct, 680°C; 36 pct, 890°C; 58 pct, 850°C; and 72 pct, 900°C. An allotropic transformation and a composition range were observed for the SmZnz compound. The transfor)nation varies from 905" to 865°C as the zinc content increases from 16.0 to 48.5 wt pct, respectively. The free energy of formation of the compounds at 50PC varies between -15.9 kcal per mole for SmZn to -51.1 kcal per mole for SmZn,.,. Corresponding enthalpies vary between -19.2 to -78.3 kcal per mole. The ther-modynamic properties for the liquid alloys are described by the relations: A search of the literature revealed very little information on the Sm-Zn system. Chao et al.&apos; as well as Iandelli and palenzonai have reported the structure of SmZn to be cubic B2 type and Kuz&apos;ma et al3. have reported the structure of -sm2zn17 to be of the Th2Ni17 type. The purpose of this work was to establish the phase diagram of this system, to determine the zinc vapor pressure over the solid two-phase regions of the SYstem, and to calculate the thermodynamic properties of the compounds. MATERIALS AND EXPERIMENTAL PROCEDURES The metals used in this investigation were Bunker Hill slab zinc 99.99 wt pct pure and Ames Laboratory samarium. Analysis of the samarium by chemical, spectrographic, and vacuum-fusion methods gave the following average impurities in ppm: Nd, <200; Eu, <100; Gd, <100; Y, <50;Ca, 225; Ta, 400; Mg, 10; Cu, ~50; 0, 175; H, 20; and N, 15. The elements Fe, Si, Cr, Ni, Al, and W were not detected. The samarium was received as sponge metal and was kept under argon except when being cut with shears and when being weighed. Tantalum was found to be a suitable container for alloys with zinc contents up to the Sm2Znl, stoichio-metry. At higher zinc contents the grain boundaries of the tantalum containers were penetrated by the alloy and the containers failed during prolonged annealing. About 25 g of massive zinc and samarium sponge were sealed in tantalum crucibles equipped with thermocouple wells. These crucibles were in turn sealed in stainless-steel jackets. All closures were made by arc welding under an argon atmosphere. The samples were equilibrated in an oscillating furnace and in some cases were given various heat treatments in a soaking furnace. After appropriate heat treatment the steel jackets were removed and the alloy subjected to differential thermal analysis. The apparatus was calibrated against pure zinc and pure copper and found to reproduce the accepted melting points within 1°C. Alloys were subsequently subjected to metallographic examination and those of appropriate compositions were used for X-ray diffraction analysis and for zinc vapor pressure determinations. The vapor pressures were determined by the dewpoint method. Both the differential analysis and dewpoint measuring apparatuses have been described in earlier papers.4, 5 All alloy samples were etched with Nital (0.5 to 3 pct nitric acid in alcohol) except the samarium-rich alloys. These more reactive alloys were electro-polished in a 1 to 6 pct HClO4 in methanol solution at -700c at a potential of 50 v. EXPERIMENTAL RESULTS Phase Diagram. The results of thermal analysis are indicated by the points on the phase diagram, Fig. 1. Eight compounds and four eutectics were observed. The composition of the compounds and their melting or peritectic temperatures are given on the phase diagram. The four eutectic compositions in wt pct zinc and eutectic temperatures in % are: 12 pct,- 680°C; 36 pct, 890°C; 58 pct, 850°C; and 72 pct, 900°C. The stoichiometry of the most zinc-rich compound is still uncertain, but is very likely either SmZnll or SmZnlz. However, to simplify the presentation which follows it will be referred to as SmZnll. As shown on the phase diagram the phase regions for some of the samarium-rich alloys have not been unambiguously established. A sample of pure samarium was observed to transform at 924°C and to melt at 1074"C, in good agreement with corresponding val-

Jan 1, 1968