Search Documents

By Donald L. Katz

FIFTEEN years ago Dr. Manning published a paper in "Petroleum Development and Technology" on '.Fundamental Research Relating to Petroleum." He tabulated for several industries "the proportion of their present success which can be fairly attributed to the application of information and processes obtained by scientific research," giving petroleum a score of 7 compared to 100 for the electrical and coal-tar industries. Today the petroleum industry as a whole and the producing groups both have raised their score beyond the majority and are climbing toward the top. Present practices are being developed both by fundamental research and the application of the research method in field operation.

Jan 1, 1941

By AIME

After an adventurous past-four changes of government in thirty years -the whole of Silesia and attached coal territories have become part of the Polish State. The coal resources of this area are the biggest among the European countries. Under a surface area of 5700 sq km are about 100 coal seams, with a total thickness of 150 meters. According to German estimates, there are some 150 billion metric tons of coal ranging in thickness up to 14 m within a depth of 1500 m. The seams are mostly level, free from faults, with good top and bottom; the coal is of excellent quality, hard and clean; and mining conditions are favorable. The mines are worked at considerable depth by means of vertical shafts and operate with cage and skip hoisting. Before the war, the mines were up to date, equipped with modern machines. Among the European countries, output per man shift was the highest ? 1.9 to 2.1 metric tons ? and cost of production was the lowest.

Jan 1, 1949

By Paul Pietrokowsky

THE formation of intermediate phases in the solid state reaction of titanium with silicon, germanium. and tin (of subgroup 4B in the periodic table) was the subject of a recent paper.' Further investigation of the system Ti-Sn revealed the presence of a new compound on the titanium-rich side of this phase diagram. Metallographic evidence indicated that this new phase was situated very close to 75 atomic pct Ti. The present work is concerned with the crystal structure of the intermediate phase Ti3Sn. Iodide-process titanium metal, furnished by the New Jersey Zinc Co., was used in this investigation. The metallic tin was received in powder form from Charles Hardy Inc., New York; its purity was 99.80 pct. The titanium rod was machined into small cups 1 cm in diam and about 1.5 cm in height. The tin powder was compacted, melted, and then placed in the titanium cups and alloyed by electric arc melting in a helium atmosphere. The alloys, weighing approximately 8 g, were sealed in evacuated quartz tubes and homogenized at 1030°C for 5 days. This isothermal heat treatment was terminated by a water quench from the soaking temperature. Filings of the alloyed pellets were sealed in evacuated quartz bulbs and quenched from 1030°C into liquid argon. A 14.32 cm Debye Scherrer X-ray camera was used for the powder diffraction study. The copper radiation was filtered. X-ray diffraction data for the compound Ti3Sn are given in Table I. The data were indexed on the basis of a hexagonal lattice. Good agreement between observed and calculated values of the square of the reciprocal interplanar spacings was obtained with the following expression: (1/d)2 = 0.03810 (h2 + hk + k2) + 0.04410 (l2) Unit cell parameters were calculated by the method of least squares from the reflections (20.3), (22.2), (40.1), and (42.1); ao = 5.916 & 0.004A, co = 4.764 ± 0.004A, and co/ao = 0.805. The relatively small size of the unit cell allowed the unambiguous indexing of most of the reflections from planes of large spacing. An inspection of the assigned indices (Table I) reveals the absence of (hk.l) reflections when 1 2n. A systematic absence of this type leads to the space group C 6/mmc or one of its subgroups. Assuming, for a first approximation, a linear increase in the density of titanium with the addition of tin, it follows that there are two stoichiometric molecules of Ti3Sn per unit cell. The density calculated from X-ray measurements is 5.194 g cm-'. At this point it became clear that Ti3Sn might be isomorphous with Mg3Cd. The 6 Ti and 2 Sn atoms were placed in the following positions of space group D4 6h, C 6/mmc: 6Tiin (h): X 2X 1/4; 22;; 1/4;Xx 1/4;x2x3/4; 2x x 3/4; x x 4; with x = 516 2 Sn in (c): 1/3 2/3 1/4; 2/3 1/3 3/4.

Jan 1, 1953

By T. J. Koppenaal, M. E. Fine

A yield point effect attributed to short-range ordevi?g (SRO) occurs in Cu base Al. At at 296°K varies with heat treatment, decreasing as the annealing ternperature is raised .from 433Oto 598°K. Davies aid Cahn' observed a corresponding decrease in SRO. (523 °K anneal, measured at 77°K) is approximateZy proportional to the variations of A7 with strain rate and testing temperature are also Consistent with the idea that is associated with SRO. A preliminary investigation of the tensile properties of a Cu-Al single crystals showed the presence of a rather strong yield-point effect (drop in flow stress after initial yielding). The object of this research was to investigate its origin and behavior. a Cu-Al alloys are particularly interesting because diffuse X-ray scattering measurements by Davies and Cahn,' Houska and Averbach,' and Borie established the presence of short-range order. The degree of local order may be changed with heat treatment.' cottrel14 suggested that the presence of local order might result in a yield-point effect, and thus the possibility exists here for experimentally ascertaining the importance of short-range order with respect to yield points in these alloys. Since a 12 pct difference exists between the atomic sizes, elastic or Cottrell locking5 must also be considered. Further, Howie and swanne have shown that the stacking fault energy of copper is reduced by aluminum additions. The width of extended dislocations should thereby increase. hus the conditions appear attractive for Suzuki locking.' Finally, the possibility of stress-induced order at dislocations, schoeck locking,' must also be examined, EXPERIMENTAL PROCEDURE Alloys up to 14 at. pct Al were prepared by induction melting high-purity (99.999 pct) Cu and (99.996 pct) Al in a graphite boat under a dynamic vacuum of 5 X 10o mm of Hg. After homogenizing the ingots at 900°C for at least 24 hr under vacuum, they were rolled with intermediate anneals to strips 1.55 mm thick. Single crystals 10 in. long were grown by lowering strips, contained in a split graphite mold sealed in fused quartz at 5 X lo-' mm of Hg, through a single coil induction heater at a constant rate of 1/2 in. per hr. Tensile specimens 1.25 in. long were cut from the single crystal strips and reduced cross sections about 0.7 in. long and 3.0 to 3.5 mm2 in area were introduced by filing and abrading.8 To remove the worked portion about 10 pct of the cross-sectional area was removed by etching. Back-reflection Laue photographs of a filed and etched specimen were taken before and after annealing at 900°c for 24 hr. Small, well defined Laue spots were obtained with no visual difference in the two photographs. Further, specimens with and without the reduced sections began yielding at about the same stress. Hence, for our purposes, filing and abrading did not affect the structure of the specimens. Each single crystal specimen was annealed at 900° c in vacuum for at least 24 hr and furnace cooled; while cooling through the range of 250o to 200°c, the rate was about 55°C per hr. Orientations were determined by the usual back-reflection Laue

Jan 1, 1962

By D. Harrington

ANNUAL or necessary inspections and investigations of coal mines for various purposes were made possible through the Federal Coal Mine Inspection Act of May 7, 1941, which authorized entry to the Secretary of the Interior through the Bureau of Mines. Primary object of these inspections is to obtain information pertaining to health and safety conditions. Among the purposes for which the data are to be used, are annual reports to Congress, the publication of inspection reports, and the compilation and publication of statistics. The act states that inspections and investigations shall be made by employees of the Bureau of Mines, who shall co-operate with other bureaus of the U. S. Department of the Interior, as well as with the official mine-inspection, safety cr health agencies of the several states and territories. The act specifies that a coal-mine inspector shall have "the basic qualifica-

Jan 1, 1946

By L. A. Roe, E. A. Elevatorski

Wollastonite, named after William H. Wollaston, an English chemist, is a calcium metasilicate, CaSiO3; CaO: 48.30%, SiO2: 51.70%. It has a short history as an industrial mineral. The earliest production of wollastonite is reported to be from a deposit near Code Siding, located north of Randsburg, CA. At this locality small tonnages of wollastonite were quarried during 1933-34 and 1938-41, and processed into mineral wool. This operation was largely experimental and virtually no United States production was again reported until the 1950s when a large deposit near Willsboro, NY, was developed by the Cabot Corp. A processing plant was placed onstream in 1953, with nearly continuous production to date. It is currently operated by NYCO, a division of Processed Minerals, Inc. Since 1958, wollastonite deposits in the Little and Big Maria Mountains of Riverside County, and in the Panamint Range of Inyo County, both in California, have operated intermittently for production of both ornamental and commercial wollastonite. During 1980, the United States was the major producing country, furnishing about 75% of the world's output. Current production comes from Finland, Mexico, India, and Kenya. Small amounts have been shipped intermittently from the USSR, New Zealand, Republic of the Sudan, Republic of South Africa, and Namibia (South-West Africa). The principal use of wollastonite is in the manufacture of plastics. Other uses are for paints, ceramics, adhesives, fluxes, glazes, thermal insulation board, and refractory products. Mineralogy Pure wollastonite, CaSiO3, has the composition of 48.3% CaO and 51.7% SiO2. However, it is seldom found in the pure state due to the ease with which it takes into solution the metasilicates of manganese, magnesium, iron, and strontium. Predominantly, wollastonite occurs as a contact metamorphic deposit forming between limestones and igneous rocks. Commonly associated minerals are garnet, diopside, epidote, calcite, and quartz. It has a specific gravity of 2.8 to 3.0, and hardness of 4.5 to 5 on Mohs' scale. When pure, it has a brilliant white color, but with impurities it may be grayish or brownish. Luster is vitreous to pearly. Melting point of wollastonite is about 1540ºC. Wollastonite occurs in coarse-bladed masses, rarely showing good crystal form. It is usually acicular or fibrous, even in the smallest of particles. The most unique property of crushed and ground wollastonite is its cleavage. Fragments of crushed wollastonite tend to be needle-shaped, imparting a high strength, and this property is the basis for many of its uses. The fiber lengths are commonly in the ratio of 7 or 8 to 1, length to diameter. The average diameter of wollastonite is 3.5 µm. Some crystals of wollastonite fluoresce under short-wave or longwave ultraviolet light, or both, with colors ranging from yellow-orange to pink-orange. Specimens may also show phosphorescence. The acicularity of wollastonite is a property of considerable importance to the marketplace. The plastics industry makes utilization of high aspect ratio grades of wollastonite (20:1) for reinforcing thermoplastics and thermoset polymer compounds. The naturally high pH of 9.9 (10% water slurry) is a prime property to the coatings industry. The coatings industry uses milled grades of wollastonite as a pH stabilizer in interior and exterior PVA and acrylic latex systems. Processed wollastonite can have a G.E. brightness of 90 to 93. Chemically, wollastonite is inert and this property makes it useful as a filler and reinforcing agent. There are two polymorphs of calcium silicates: wollastonite, a low temperature form, and pseudowollastonite, a high temperature

Jan 1, 1983

By L. D. Jaffe, R. K. Pitler

IT would clearly be advantageous to produce molten titanium, suitable for alloying and casting, directly from the relatively inexpensive tetra-chloride, without using a metallic reducing agent. Accordingly, a preliminary investigation has been made of the production of titanium by hydrogen reduction of the tetrachloride in an electric arc furnace. For the reaction: TiCl4(g) + 2H2(g) ? Ti(s) + 4HCl(g), Lockhart and his colleagues' have calculated equilibrium constants at 800" to 1500°K, based on tables of Brewer.' Extrapolating these data on the assumption that the heat of reaction varies linearly with temperature, and using Brewer's value for the heat of fusion, there is obtained for the reaction: TiCl4(g) + 2H2(g) ? Ti(l) + 4HCl(g) an equilibrium constant at 2100°K (100" above the melting point) Kp = (PHCl)4/pTlcl4 (Ph2)2 = 0.167 atm. If this is correct, starting with hydrogen saturated with TiC14 at 25°C, where the vapor pressure of the latter3 is 12.6 mm, and maintaining the overall pressure at 1 atm, 99 1/4 pct of the TiC14 would be reduced to Ti at equilibrium. An arc furnace designed for the melting of titanium and lined with water-cooled copper was used for the preliminary experimental check. Its inside diameter was 2 7/16 in. and height 6 in. The water-cooled electrode was tipped with 3/4 in. diam tung-sten. In the one run carried out, the furnace was charged with a starting batch of 293.35 g of scrap titanium,' analyzing 99.24 pct Ti. After the system was twice pumped out and flushed with argon to remove air, the arc was struck in argon and kept at 400 amp dc, electrode negative, for 1 min to melt the starting batch. Commercial tank hydrogen, dried by passing over silica gel and bubbled through technical grade TiC14 at room temperature, was then admitted to the furnace. The inlet tube directed this gas downward toward the arc and melt; the gas outlet was at the top of the furnace. The quantity of gas passed through was not measured accurately but is estimated to be about 50 liters per min at a few mm of mercury above atmospheric pressure. The arc was held in the H2-TiC14 mixture at 400 amp with little difficulty. After 10 min the arc burned through the copper lining above the melt, admitting water and ending the run. (This had happened frequently in straight melting runs under argon, and is not thought due to the atmosphere used.) In the furnace were found an ingot, several small pieces, and a little metallic powder, evidently formed when water entered the hot furnace. Some titanium also clung to the electrode. The portions were weighed and separately analyzed for titanium. Their total weight was 321.76 g of 94.82 pct overall purity. Much of the impurity consisted of tungsten broken off when the titanium was removed from the electrode. No detailed impurity analysis was made because the starting materials were impure and flooding the furnace introduced further contamination. Thus, the metal recovered contained 305.08 g Ti, as compared to 291.12 g in the starting batch. Titanium could not have been carried over from previous melting runs in the furnace, as the interior was sandblasted and the electrode ground clean before the run. Evidently at least 13.96 g of Ti were produced from TiCl4. Since this would require complete reduction of 430 liters of TiCl, gas at 12.6 mm of Hg, the efficiency of the process must have been rather high. Experimental work is continuing. No reason is seen why the process could not be scaled up to the size of a 30-ton steel-melting arc furnace. In a large unit there would be a large molten pool from which liquid metal could be withdrawn for alloying and casting. The problems of electrodes and power supply are similar to those arising in arc furnaces for melting titanium. Unreacted TiC14 and the HC1 in the exhaust gases could be recovered; unreacted H2 could be dried and re-used. The melt would be saturated with hydrogen, whose solubility in liquid titanium is unknown. Small amounts of hydrogen seem to have little effect on the properties of titanium.5 If the amount introduced was so large as to impair properties or cause casting difficulties, it could be reduced by holding the melt under an inert gas or by pumping on it, prior to casting. Acknowledgment The authors would like to thank I. Preble and M. Goldman for their valuable aid in the experimental work and the thermodynamic calculations, respectively. References 1R. J. Lockhart, J. J. Ward, M. J. Hussey, and J. W. Clegg: In unpublished report, "U. S. Air Force Project Rand. Titanium and Titanium Base Alloys." Battelle Memorial Institute (1949) 37-44. 2 L. Brewer et al: Chemistry and Metallurgy of Miscellaneous Materials—Thermodynamics. Ed. by L. L. Quill. pp 13-39, 60-192. (1950). McGraw-Hill Book Co. 3 K. Arii: Scientific Reports. Tohoku Imp. Univ. (1933) 22, 182. 4 R. S. Dean, J. R. Long, F. S. Wartman, and E. L. Anderson: Transactions AIME (1946) 166, 369-381; Metals Technology (Feb. 1946) TP 1961E. * R. I. Jaffee and I. E. Campbell: Transactions AIME (1949) 185, 646-654; Journal of Metals (Sept. 1949) TP 26813.

Jan 1, 1951

By K. P. Mukherjee, K. P. Gupta, J. Bandyopadhyaya

Even though a lot of work has been done in the past to establish phase equilibrium in the Cu-Si system a re cent investigation casts some doubt about the existence and crystal structure of some of the phases that form in the composition range of 15 to 25 at. pct Si in Cu. The present investigation was carried out using high temperature X-ray diffraction technique along with other standard techniques to study the phases in this composition range. The high temperature 6 phase appears to be tetragonal with parameters a,, = 8.815A, c, = 7.903A, and co/ao = 0.896. The reported bcc E phase exists at room temperature and at least up to 780°C and appears to undergo a transformation near 600°C. The phase appears to be cubic but not of the bcc type. The ? phase appears to undergo a transformation, as has been indicated by earlier investigators, and the low temperature form of .? phase is tetragonal with parameters a, = 7.267A, co = 7.8924, and co/ao = 1.086. THE Cu-Si binary system has been investigated by several investigators1" and several intermediate phases,?,e,?' at lower temperatures and ?,ß,0,e, and ? at higher temperatures, were observed between terminal solid solutions of copper and silicon. Even though the existence of the e phase and the transformation in the ? phase were reported in many early works, in a recent study of this system Nowotny and Bittner6 doubted the existence of the e phase and phase at 550°C. Among the high temperature phases, the 6 phase was reported to have a complex cubic structure with parameter a, = 8.805A.7 Nowotny and Bittner, however, suggested that the structure of the 6 phase might be of CsCl type. In order to check these contradictory reports the present study was taken up to investigate the Cu-Si binary system in the composition range of 17 to 25 at. pct Si. EXPERIMENTAL PROCEDURE Weighed amounts of copper (99.99 pct) and silicon (99.9 pct) were induction melted in recrystallized alumina crucibles under argon gas atmosphere. The alloys containing 17, 18, 20, 21, 21.2, 22, and 24 at. pct Si were annealed in evacuated and sealed quartz capsules at 700°C for 3 days and subsequently water quenched. Other than this annealing, the 21.2 at. pct Si and 24 at. pct Si alloys were annealed at 550°C for 10 days, the 17 at. pct Si alloy was annealed at 750°C for 3 days, and the 22 and 24 at. pct Si alloys were annealed at 780°C for 2 days. All annealing temperatures were controlled to within *l°C. Alloys after quenching were subjected to metallographic and X-ray diffraction investigation. A solution containing 5 g FeC13 + 10 cc HCl + 120 cc H2O diluted with six times its volume with water was used as etching reagent. A 114.6 mm diam Debye Scherrer camera was used for obtaining diffraction patterns. The 17, 21.2, and 24 at. pct Si alloys were subjected to high temperature diffractometry using a Tempress Research High temperature attachment and a GEXRD VI diffractometer. For the 6 phase (17 at. pct Si alloy) powder specimen from a 750°C annealed alloy was reheated to 750°C in the high temperature attachment for 1½ hr before taking a diffraction trace. A 550°C annealed and slowly cooled phase (24 at. pct Si) alloy was first reheated to 550°C. a diffraction trace was made after annealing it for 2 hr, and subsequently it was heated to 716OC and kept at this temperature for 2 hr before taking a diffraction trace. For the e phase (21.2 at. pct Si alloy) a 550°C annealed and slowly cooled specimen was heated first to 425°C and annealed at this temperature for 2 hr before taking a diffraction trace. Subsequently, the specimen temperature was raised to 495", 540°, 603", 635", 682", 720°, and 748°C and homogenized at each temperature for 1 hr before taking diffraction traces. The powder specimen temperature was controlled to within +2oC at each temperature and argon gas, purified by passing it at slow rate through a fused CaC12 column, hot (800°C) copper and titanium chips and finally through a P2O5 column, was used to prevent oxidation of the powder. For all X-ray work copper-radiations at 25 kv, 15 ma (for Debye Scherrer technique), and 40 kv, 20 ma (for diffractometer tech-nique) were used. RESULTS AND DISCUSSION At 700°C the alloys containing 17 to 21 at. pct Si showed two phases while the 21.2 at. pct Si alloy was found to be single phase. The X-ray diffraction patterns of the two-phase alloys were consistent with the phase (ßP-Mn type structure) and the phase (21.2 at. pct Si) patterns. The diffraction patterns of the 17 at. pct Si alloy quenched from 750" and 700°C were identical. According to the accepted Cu-Si phase dia-gram4,5,10 the 17 at. pct Si alloy at 750°C should be in the (k + 6) two-phase region and very close to the -phase boundary. The identical patterns possibly resulted from the decomposition of the 6 phase on

Jan 1, 1970

By W. Mckewan, W. M. Fassell

The oxidation rates of copper have been determined at temperatures from 600" to 900°C in oxygen from 14.7 to 400 psi total oxygen pressure. The oxidation rate of copper is unchanged by oxygen pressures within the range studied. The observed data extend Feit-knecht's conclusion concerning the pressure independence of copper from atmospheric pressure to 400 psi. All samples studied in the above-mentioned temperature and pressure range have both Cu2O and CuO present in the oxide film. NUMEROUS papers have been published on the oxidation of copper, some of which have noted the effect of oxygen pressure on the oxidation rate of copper. It must be noted, however, that no data on the oxidation rates of copper at pressure in excess of 1 atm have been reported in the literature. (Le Chatelier¹ reported that a black oxide of silver was formed at 300°C and 15 atm pressure.) This is likewise true for the other metals. This investigation was initiated to obtain experimental oxidation rate constants for pure metals at elevated temperatures and high oxygen pressure. Copper was selected as the first metal since probably more reliable data are available on its oxidation rates and related physical and chemical properties than for any other metal or alloy. As a general summary, the following conclusions appear well established for the oxidation of copper: 1—The oxide coating consists of Cu2O with a superficial coating of CuO providing the ambient oxygen pressure exceeds the equilibrium pressure for the coexistence of Cu2O and CuO.² The following sequence of phases is then Cu/Cu2O/CuO/O2 (gas). The Cu2O consists of large crystals that have no relation to the orientation of the metal crystals, except for a very thin layer adjacent to the metal." The CuO consists of very fine crystals randomly oriented. If the oxygen pressure is below the equilibrium pressure for the coexistence of Cu2O and CuO, the coating consists of Cu,O only. 2—The rate-determining factor in the parabolic oxidation of copper is the diffusion of Cu+ ions through the Cu,O layer.4,6,7 The Cu+ ions are accompanied by electrons to maintain electrical neutrality. The mechanism of the reaction at the Cu2O/CuO interface and the method of growth of the CuO is in some doubt. 3—On copper, there are three reported pressure effects: (a) At pressures below 0.3 mm Hg oxygen pressure, the oxidation rate increases directly with pressure.', ' .Vxygen starvation at the surface may account for this effect. (b) At oxygen pressures from 0.3 to 63 mm, the oxidation rate increases as the 7th root of the oxygen pressure providing the temperature is such that only Cu2O is present in the film. (c) At pressures from above the equilibrium pressure for the coexistence of Cu2O and CuO (varies with temperature) to atmospheric pressure, the oxidation rate is independent of the oxygen pressure.' Equipment In order to determine the oxidation rates of metals in an oxidizing atmosphere at pressures up to 400 psi, the equipment is somewhat different than for low pressure work as is shown in Figs. 1 and 2. A Leeds and Northrup Micromax recording controller (A) is used to control the temperature of the Ni-chrome furnace winding in conjunction with a Micromax electric drive unit. The drive unit adjusts a 20 amp Variac (variable transformer) to control the power input into the Nichrome furnace winding. Due to the "self heating" of the sample by oxidation, frequently encountered in oxidation rate studies, it is essential that the sample temperature be measured independently. This is done by means of a series of six chromel-alumel calibrated thermocouples located spirally around the oxidizing metal sample. Each thermocouple is partially shielded from the direct radiation of the furnace wall by

Jan 1, 1954

By C. G. Bieber, J. R. Mihalisin, R. T. Grant

A growing demand for longer service life of gas turbines has placed increasingly rigorous requiret~rents upon superalloys employed for that application. Long-titne testing at high temperature has revealed that phase transformations occur in all superalloys. A common one of particular interest is o formation. Presented here are studies made to identify a and to characterize its formation and effect on properties in three cast nickel-base superalloys—IN 100 alloy, alloy 713C, and alloy 713LC. Methods are discussed by which o can be eliminated or inhibited in IN 100 alloy and alloy 713C. Evidence was obtained to indicate that some types of o may be more detrimental than others. Limitations in the electron vacancy approach to o prevention are pointed out, and it is shown how alternative approaches, such as reducing a complex superalloy matrix to the form of a pseudo-ternary system permitting equilibrium diagram treatment, lead to additional insights into the formation of in these alloys. AROUND 1960. Beiber1 developed IN 100 alloy, which still remains one of the strongest commercially available nickel-base superalloys. The principle used in the design of this alloy was to produce large quantities of y' phase in a y matrix through the use of copious amounts of aluminum and titanium. In 1963, ROSS' showed that when certain heats of this alloy were held for a long time at 1650°F they formed an acicular phase, subsequently identified as a.3 a is a hard and brittle phase first discovered in the Fe-Cr system by Bain and Griffiths.4 They termed it the "B" constituent. Subsequently this same phase was found in other systems, primarily those of the transition elements, and acquired the name "a" by which it is now known. The crystal structure of the a phase was first determined in the Fe-Cr system in 1950.5 It was shown to be tetragonal with a c/a ratio of about 0.52. as is the case with a found in other systems. This characteristic crystal structure is now the means by which a is identified. In superalloys, such as IN 100 alloy. large amounts of o impair the high-temperature creep strength and drastically reduce room-temperature tensile ductility. Discovery of o phase in some heats of IN 100 alloy quickly led to investigations of other superalloys for similar transformations. It was found that many of the stronger, more highly alloyed. super-alloys were indeed susceptible to o formation. This investigation has been concentrated on three commercial alloys: IN 100 alloy, alloy 713C, and alloy 713LC. J.R.MIHALISIN,MemberAIME, and C.G.BIEBER are with The International Nickel Co., Inc., Paul D. Merica Research Laboratory, Sterling Forest, Suffern, N. Y. R. T. GRANT, Member AIME, is with The International Nickel Co., Inc., Pittsburgh, Pa. Manuscript submitted May 22. 1968. IMD A detailed study has been made of the phase transformations and their relation to a formation along with a consideration of electron vacancy approaches for predicting a-forming propensity in these alloys. EXPERIMENTAL PROCEDURE Phase transformations were studied by light and electron microscopy, electron diffraction, microprobe investigations, and X-ray diffraction. Specimens for light micrographic examination were prepared by conventional grinding and polishing followed by etching with glyceregia (2:l HC1/HNO3 + 3 glycerine by volume). Photomicrographs of stress-rupture specimens were taken adjacent to the fracture unless otherwise noted in the text. Negative replicas for electron microscopy were taken from surfaces electropolished with a solution of 15 pct H2SO4 in methanol. For carbon extraction replication, a solution of 10 pct HC1 in methanol was used. A Siemens Elmiskop I was used for all electron microscopy. Selected-area diffraction studies were made at 80 kv using evaporated aluminum for standardizing the patterns. A nondispersive electron microprobe attachment was used to analyze the extracted precipitates chemically. The fluorescent X-rays were recorded using a flow counter containing P10 gas (90 pct Ar-10 pct methane) with a beryllium window and a single-channel pulse-height analyzer. The pulses from the analyzer were passed to a scaler-ratemeter and differential curves of counting rate vs pulse amplitude were obtained. The base line of the analyzer was driven with a synchronous motor at 0.5 v per min and a channel width of 0.5 v. The time for 105 counts was printed out for each 0.5-v increment. The microscope was operated at 80 kv with beam currents of 1 to 20 pa. This equipment detects elements from atomic number 13 to 40. X-ray diffraction studies were usually made on residues electrolytically extracted in 10 pct HC1 in H2O, although in one case a pattern was obtained from an etched surface of a metallographic specimen. A Siemens Crystalloflex IV was used with iron-filtered CoKa radiation. X-ray patterns were recorded using a goniometer speed of : deg per min. The scintillation counter and pulse-height analyzer operated at a channel height of 10 v and a channel width of 12 v. The equipment was calibrated with a powdered gold standard. The residues usually contained a number of phases. several of which could not be found in the ASTM card file. In addition, as is shown for the case of a phase in IN 100 alloy, other phases had a somewhat different lattice parameter from that reported in the ASTM card file, making it difficult to separate and identify constituents by comparison with ASTM d spacings. For these reasons, phases were identified on the basis of the lattice parameter obtained by indexing the ob-

Jan 1, 1969

By Philip D. Wilson

SPEED is essentiaI in this war program and it is hard to keep up with developments. When the title of this paper was chosen, the contemplated magnesium production for which plants were then under construction was some 200,000 tons of metal per year or sixty times the 3350-ton production in prewar 1939. A few- days later an analysis of the President's 185,000-plane pro-gram, incendiary bomb schedules, and the additional requirements of the Army. Navy and Maritime Commission made it apparent that a much greater amount of magnesium must be provided in 1943. The new figures are huge but the censor will not per-mit their disclosure.

Jan 1, 1942

Mine Taxation On Monday morning, Sept. 22, a session on- Mine Taxation was held in cooperation with the Internal Revenue Dept., U. S. Treasury, Mr. R. C. Allen presiding. This was followed by two adjourned sessions, at which Mr. R. C. Allen and Mr. A.D. Brokaw presided. The following paper was presented: Federal Taxation of Mines. By L. C. Graton. (Presented by the author; dis¬cussed by R. V. Norris, W. O. Hotchkiss, W. P. Beldon, Paul Armitage, R. C. Allen, E. F. Brown, William Belly, A. D. Brokaw, F. W. Sperr, C. H. Benedict, E. P. Griffitts, W. E. Forsythe, and the author). Coal and Gas The first session on Coal and Gas was held on Monday morning, Sept. 22; the second, on the afternoon of the same day. Mr. Curl Scholz presided at both sessions. The following papers were presented: Research on the Coal-mining Industry. By E. A. Holbrook. (Presented by the author.) Some Factors that Affect the Washability of a Coal. By Thomas Fraser and H. F. Yancey. (Presented by the author.) A Use Classification of Coal. By George H. Ashley. (Presented by title.) Distribution of Anthracite. By A; S. Learoyd. (Presented by title.) Height of the Gas Cap in the Safety Lamp. By C. M. Young. (Presented by the author.) Engineering Features of Modern Large Coal Mines in Illinois and Indiana. By C. A. Herbert and C. M. Young. (Presented by the authors.) Gas-producer Practice. By G. S. Brooks and C. C. Nitchie. (Presented by the authors.) Testing of Coals for Byproduct Coking and Gas Manufacture. By Horace C. Porter. (Presented by the author.) Coals of Ohio and their Limitations for Byproduct Coke. By Wilber. Stout. (Presented by the author.) Outdoor Substations in Connection with Coal-mining Installations. By H. W. Young. (Presented by the author.)

Jan 11, 1919

By Frank G. Breyer

THE .following developments in the zinc field during 1935 are listed in the order of their importance. Each will he amplified in later paragraphs. In the field o f Metallic Zinc: (1) Construction of further continuous vertical retort smelting capacity in the United States and Germany. (2) Expansion of fractional distillation capacity in the United States. (3) Great expansion in the zinc-base die-casting industry in the United States and abroad. (4) Wide acceptance of heavy galvanizing by the steel industry. (5) Construction of the first commercial wire electroplating plant for putting on heavy coats of pure zinc. (6) Firm establishment and appreciable expansion of the practice of using zinc dust as a reducing agent in the organic chemical industry.

Jan 1, 1936

By W. M. Ross

AMONG the comparatively few A radical changes in mining equipment in recent years is the introduction and use to an ever greater degree of detachable bits for rock drills. Just how great the possible field for economic application of this innovation is, and to what ex- tent detachable bits are used instead of the conventional type of drill steel, are matters of conjecture. Just as a rough approximation, one might conceive that at least three-quarters of the drilling done in mines today could better be performed by steel with detachable bits, instead of only about one-quarter as at present.

Jan 1, 1939

By H. H. Campbell

MANY attempts have been made to write a formula by which to calculate the strength of steel from its chemical composition, but most of these endeavors have failed because there were too many disturbing conditions. It is idle to collect from the pages of trade-papers, books, or the proceedings of scientific societies, a multitude of observations. The combination of such results will simply show that steel of the same composition will vary in tensile strength through wide limits-a fact that has been known for generations. That cold-working, overheating, and many another form of heat-treatment alter fundamentally the strength of steel, is ancient history, although it is only recently that the microscope has pointed out the road to an explanation of the phenomena. It may be urged that the microscopic structure must be taken into consideration in any formula giving the ultimate strength, but from the standpoint of the present investigation this is unnecessary. We are trying to determine primarily, not what changes in ultimate strength may be made by variations in the condition of carbon, but what effect is produced by changes in the amount of carbon, when its condition remains constant. For such an inquiry, in order that the condition of the carbon should remain as nearly uniform as possible, it is essential that all test-pieces be made under the same conditions; and it is be¬lieved that the tests described in this paper satisfy that require¬ment. The investigations were made at the works of the Pennsylvania Steel Company,. Steelton, Pa.; the ingots from which the tests were made were 6 in. square in every case; they were heated in the same furnace and forged at the same ham

Jan 1, 1905

By L. F. Pett

ALTHOUGH Kennecott's orebody has long been outlined, it is still necessary to define further its limits. This mine, long an advocate of churn drill methods, recently supplemented its practice by using a diamond drill. So far, the diamond drill holes have been along the main canyon floor which traverses the mine area. This zone, highly fractured, is cut by numerous friable quartz veinlets encountered within the porphyry. These veinlets, formed by filling contracted porphyry fractures with hot, siliceous, mineral-bearing solutions, are often more highly mineralized than adjacent porphyry. They pulverize on contact, yielding only slight amounts of core. For this reason neither analysis of core recovered (amounting to 37.5 pct of approximately 10,000 ft of hole drilled) nor sludge analysis considered separately would give correct assays. The following equation has been adopted: actual weight theoretical actual weight core — theoretical weight sludge Drilling is done un.der contract. Collection of core and sludge samples together with double-checked assaying is done by the company. Microscopic, specto-graphic, and X-ray examination of rock specimen saved is carried on at the University of Utah. A fund, set up by Kennecott Copper Corp. at the University, has encouraged cooperation in solution of mining research problems. The drill used is a Longyear hydraulic powered by a Waukesha 26-hp gasoline motor. A pump, Bean Royal type, is powered by a 7-hp Briggs-Stratton gasoline motor. Weight of unit is 4000 lb and is placed under tripod of 35-ft wood poles within a 25-ft sq area. The following results have been attained: Avg depth of hole drilled, ft 1215 Avg drilling depth per 8-hr shift, ft 10.11 Core Size, In. Avg depth of NC casing, ft 21 2 11/16 Avg depth of NX casing and size core, ft 178 2Ye Avg depth of BX casing and size core. ft 427 1% Avg depth of AX casing and size core, ft 585 1 5/32 Through the use of metal sludge collection boxes, 12 ft long, 18 in. wide, and varying from 12 to 24 in. in depth, sludge recovery has been maintained above 95 pct. Samples, both core and sludge, are assembled for each sample interval and averaged in 50-ft bench increments. Determinations for mineral values are made at both the mine and mill. Assay results varying in excess of 0.05 of copper assay values are rerun to determine correct assay. The organization chart for the Kennecott Utah copper mine is shown in Fig. 1. The Utah mine requires approximately four men per shovel shift to drill solid rock, properly slope banks, and trim loose material from the top of bench sections in making them safe for men and equipment working below. During recent years, while the mine has been worked day and night, powder crews have worked day shift only. Series of toe holes drilled back of advancing electric shovels comprise approximately 70 pct of all mine drilling. These holes, spaced about 21 ft apart, have a depth of 24 ft. Of the footage drilled, 25 pct is for vertical holes either 24 or 28 ft deep, spaced about 28 ft centers along the top rim of banks. This combination of toe holes, using an Ingersol-Rand DA 35 drifter mounted on a tripod and the vertical holes using an Ingersol-Rand Type X71 wagon drill is standard practice above the pit elevation. These benches are 68 ft high, with a few exceptions, while benches below the pit elevation are 50 ft high and require very little drilling other than toe holes. Five benches, varying in height from 80 to 100 ft, require a combination of toe holes plus vertical holes and bank holes or electric churn drill holes. Bank holes using the DA 35 drifter and electric churn drill using Bucyrus-Erie Model 29T, account for 5 pct of feet drilled. Until the past year, drilling of fill material on upper levels was accomplished by churn drill method. Wagon drills are now used for fills because they can be set up and drill a hole an hour. It is necessary to run an air drill 7 hr for each 8-hr shovel shift. Average drilling rates during the past year were as follows: DA 35 drifter using 2 and 3-man crews — 4.36 ft per man hr X 71 wagon drill using 2-man crews — 6.45 ft per man hr DA 35 drifter bank holes, 3-man crews — 2.53 ft per man hr Bucyrus-Erie churn drill, 2-man crews —1.9 ft per man hr Total mine avg — 4.57 ft per man hr Mine practice assigns powdermen to job locations where they perform all drilling and blasting work within the area. Almost as much labor is consumed in springing and loading holes as in drilling them. Average powder consumption is approximately as follows: Per Electric Shovel Shift, Lb To spring and chamber holes — 50 Blasting — 500 Trim banks — 50 One fifth of all powder used is Hercules hercomite bag powder while four fifths is Hercules gelamite 65 pct strength in 1 Vi in. x 8 in. sticks. Frozen material, overhanging from top banks, creates a winter hazard to shovel operators and equipment. Experiments are being conducted with a high-speed Hercules powder in an effort to eliminate this condition. Banks are trimmed by powdermen who lodge 8 or 10 bundles of powder, containing 15 or 20 sticks each, across the upper surfaces of each working face. To each bundle of powder is attached a primer with 6-ft fuse which is lighted as the powdermen, who have lowered themselves down the bank on ropes, ascend to safety. Three angle dozers, D8 caterpillars, make grades and move supplies for the average 31 drilling machines working daily. Compressed air is furnished by three Ingersol-Rand compressors, each with rated capacity of 3750 cu ft of air per min at 100 lb reservoir pressure.

Jan 1, 1952

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 G. L. F. Powell, L. M. Hogan

Samples of silver and Ag-O alloy, 0.12 wl pet, have been undercooled to a maximum of 250°C by melting in a slag of commercial soda-lime glass. Grain refinement occurred in undercooled silver samples whet the degree of undercooling exceeded a critical value which varied from 153° to 175°C, depending on the melting conditions. In under cooled Ag-0 samples, the grain structure was fine and equiaxed at degrees of undercooling larger than 50oC. The grain refinement in both silver and Ag-0 alloy samples was the result of recrystallization during or immediately following freezing. When the oxygen content was increased, the degree of undercooling at which recrys-tallization occurred decreased. INVESTIGATIONS of the grain structure of strongly undercooled melts of nickel and cobalt1-4 have revealed a change in room-temperature grain size as a function of undercooling. At large degrees of undercooling the grain size was fine, but samples undercooled by smaller amounts exhibited a much coarser grain structure. The reported undercooling at which this grain size transition occurred in nickel varied between 140° and 175'C undercooling. Walker1 attributed this grain size change to an enhanced nuclea-tion rate. Cavitation at a melt-solid interface was con sidered to generate a high-pressure wave. This, in turn, produced nucleation in the liquid as a result of an elevated freezing point increasing the undercooling in the melt. A similar grain size transition was observed in undercooled silver between 133° and 153°C undercooling.5 The grain size transition in undercooled silver was found to be dependent on oxygen con tent. More recently, the authors5 showed that a simila transition occurred in an undercooled Cu-O alloy, =0.08 pet, but not in oxygen-free copper undercooled more than 200°C. The transition was attributed to recrystallization of the solidified grains after freezing; the greater the degree of undercooling, the more complete the recrystallization. In view of this effect of oxygen content on grain size transition, additional undercooling experiments were carried out with silver. This paper reports the results of these studies on silver and Ag-O alloys undercooled more than 50°C EXPERIMENTAL 1) Materials. The silver was supplied by Matthey Garrett Pty., Ltd., as fine granulate, silver mini' mum 99.9 pet, and contained the trace impurities shown in Table I. The silver originated from two different refineries resulting in the difference in impurity content shown in Table I. However, the variation in composition had no discernible effect on the undercooling behavior. Samples of the silver were melted in an open-ended, vertical, cylindrical resistance furnace, wound with Kantha] wire, the temperature of which was adjusted by means of a variable transformer, 2) Melting and Undercooling. Bulk samples of silver were undercooled by preoxidation and removal of oxidized impurities in a glass slag, as previously described,5 but special precautions were necessary to allow comparison between oxygen-free silver and a Ag-O alloy. Samples free of oxygen were prepared by first melting weights of granulate varying from 200 to 400 g in clean vitreous silica crucibles in air for approximately 15 min. A sample was frozen and a complete glass cover formed over the top surface by adding granulated glass rod. The sample was then melted and frozen several times until no oxygen bubbles appeared in the glass slag. Subsequent thermal analysis indicated that the oxygen content was negligible. The glass acted as an efficient barrier to absorption of oxygen from the air. Ag-O alloys were prepared by melting silver in silica crucibles with only a partial cover of glass, so that the top surface of the melt was in contact with air. The silver was held molten in air for several hours at 1000° to 1050°C, in the expectation that the oxygen in solution would reach equilibrium with atmospheric oxygen. At T - 1000°C the equilibrium oxygen content was calculated as 0.12 wt pet O, using Sieverts law and Eq, [l], derived by Mizikar et a!.7 from the data of Sieverts and Hagenacker8 for 1 atm of oxygen:

Jan 1, 1970

By Chester A. Fulton

SUPPLYING as it does a necessity for healthy animal and vegetable phosphate production is a most important industry. We human beings also are animal as this war so surely proves. Unlike many other elements no substitnite is available for phosphorus or its compounds. Marvelous as are modern plastics none can lake the place of phosphorus in making hone structures. As meassured in these times the phosphate industry is not a large industry. Output of phosphate rock, the original source of our agricultural and ,chemical phophates amounts to only some twelve million long tons per annum in the entire world. Phosphates are compounds of phosphorus, which is always found in nature combined with other elements. It never occurs in nature as such. The first choice of the element phosphorus is tie itself strongly to oxygen and then to water moisture - thus becomeing phosphlic acid. This phosphoric acid in turn hunts around for a base such as lime for instance and together they make phosphate of lime.

Jan 1, 1944

By J. S., Douglas

IN 1880, the late James Douglas, LL.D., was superintendent of the Chemical Copper Co., operating the Hunt & Douglas process for the treatment of the siliceous copper ores of the Jones mine at Phoenixville, Pa. In conjunction with this a refining furnace was operated. After correspondence with Ben Williams, of Bisbee Ariz., who was commencing the mining and smelting of the Copper Queen ore. Dr. Douglas decided-to make his first journey to Arizona. While making plans for the trip lie visited a friend in Philadelphia, a .Mr. Logan, a prominent lawyer. He, through Professor Treadwell, brother of the discoverer of the great Treadwell gold mine of Douglas Island, Alaska, had an option with his min¬ing partner, Mr. Lenig, on the Eureka and Wade Hampton claims near the headwaters of the Verde River in Yavapai County, Arizona. These two claims, later the source of practically all of the wealth of the Jerome district, were then owned by C. P. Head and Co. Prescott merchants. Hugo Richards, banker, and formerly sutler at Camp Apache; Rod and John McKinnon prospectors and Nova Scotians; and perhaps one or two 'other owners of minor interests. Mr. Logan, hearing of Dr. Douglas intended trip to Bisbee, asked him to go first to see the two mining prospects, and this, Douglas, in need of the $500 fee, agreed to do as the time on the option on the claims was running short.

Jan 1, 1935