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By J. E. Neal, C. T. Naber, O&apos

Silicon thin films were deposited by electron beam evaporation in an ultrahigh vacuum onto (0001) and (1102) sapphire substrates. Attempts were made to correlate the structural properties of the deposited silicon films with the following: 1) substrate orientation, 2) substrate surface condition, 3) substrate temperature, and 4) deposition rate. The substrate temperatures were varied between 500° and 1000°C and the deposition rates were varied between approximately 50 and 700A per min. The following sapphire surface treatments were investigated: 1) annealing in the ultrahigh vacuum at 1200° C; 2) heating in a hydrogen atmosphere at about 1350°C; and 3) etching with silicon by evaporating silicon onto sapphire substrates heated to 1200° or 1300°C. Twinned silicon films were occasionally formed at substrate temperatures between the 800° and 1000°C on unprocessed mechanically polished substrates; however, the reproducibility and crystallinity of these films were generally poor. Single-crystal and twinned silicon films were formed at substrate temperatures between 700° and 1000°C on substrates which were silicon-etched at 1300°C prior to deposition. Fiber texture films were formed at substrate temperatures between 500° and 700°C. The (111) lattice plane of the silicon single-crystal films was parallel to the (0001) sapphire plane and the (100) silicon plane was parallel to the (1102) sapphire plane. TECHNIQUES are well-established for growing single-crystal silicon thin films on sapphire by chemical methods.'-* Vacuum epitaxial techniques have a number of advantages over chemical epitaxial techniques in the fabrication of thin film microcircuits.5 One of the most significant is that vacuum techniques are compatible with well-established procedures for forming vacuum-deposited thin-film resistors, capacitors, and interconnections. Salatna, Tucker, and young6 recently reported the formation of relatively poor crystalline-quality silicon films on sapphire by electron beam evaporation in a vacuum of about 7 x 10-7 Torr. The purpose of the investigation described here is to determine the relationships between the structural properties of silicon thin films deposited on sapphire substrates by electron beam evaporation in an ultra-high vacuum and the following: 1) substrate orientation; 2) substrate surface condition; 3) substrate temperature; and 4) deposition rate. The substrate temperatures were varied between 500° and 1000° C and the deposition rates were varied between approximately 50 and 700A per min. Two orientations of sapphire were used: (0001) and (1102). The thick-nesses of the films were between 8000 and 16,000A. The morphology and crystallinity of the deposited films and substrate surfaces were investigated by optical microscopy, electron microscopy, and electron diffraction. APPARATUS AND PROCEDURE A cross section of the ultrahigh-vacuum thin-film evaporator is shown in Fig. 1. The bell jar is stainless steel and copper gaskets are utilized at all seals. High vacuum is attained by a 6001iter per sec ion pump and a titanium sublimation pump. Sorption pumps are used to rough the system to a pressure of about 10 µ prior to starting the ion pump. Vacuums in the 10- 10 Torr range were attained after baking the system at about 250°C for 8 hr. Vacuums in the 10-8 to 10-9 Torr range were maintained during silicon evaporation. The silicon charges, which were cut from p-type single-crystal boules which had resistivities between 2000 and 4500 ohm-cm, were placed in the water-cooled copper crucible of a 180 deg bent-beam 5-kw electron beam evaporator. During evaporation, a molten zone was formed in the top center of the silicon charge, and the portion of the silicon charge in contact with the water-cooled crucible remained solid. The substrate heater, which has been described

Jan 1, 1969

By A. E. Lee

THE Blackwell Zinc Co., Inc., a subsidiary of the American Metal Co., Ltd., operates a horizontal retort zinc smelter at Blackwell, Okla. The plant has 14 furnace blocks of 800 retorts each, fired with natural gas on a 48 hr cycle. Over 13,000 tons of zinc-bearing material, chiefly sulphide flotation concentrates, are treated monthly to produce slab zinc and high lead-cadmium fume. In 1942 a program of rebuilding and modernizing the smelter was started. By 1947 furnace smelting capacity had been increased to a point where roasting and sintering facilities were inadequate, and it was necessary to purchase oxidized materials to supplement sinter production. The seven 210 ft Ropp roasters and three 42 in. x 44 ft Dwight-Lloyd machines then in use had been in service at least 20 years and were in need of major rebuilding. Thus it was entirely practical to consider all new equipment and a change of method rather than rebuilding and repairing obsolete units. A study of the problem indicated that roasting as such could be eliminated and roasting and sintering accomplished in one step by a modification of the Robson process,' which had been used since the early 1930's by the National Smelting Co., Ltd., at their plants at Avonmouth, England, and Swansea Vale, South Wales. Francis P. Sinn, General Manager, Zinc Smelting Operations, The American Metal Co., Ltd., who was familiar with the practice in England, suggested the use of one large machine for the entire operation from concentrate to sinter. One step sintering appeared to best meet Blackwell's plant requirements and indicated substantial savings in labor, gas, coal, and repair costs. Choice of Machine Size The sinter machine size was set at 12x168 ft for a rated capacity of 540 tons per day. This tonnage, produced on a five day week, would meet the seven day requirements of the 14 furnace blocks. The one large machine was quoted at a lower cost than two or more 6 ft wide machines of similar total capacity. Further, the larger machine could be housed in a smaller structure and only one set of equipment for charge preparation and delivery and for disposal of sinter cake was needed. One machine on a five day week made possible a concentration of the skilled operating personnel and required less men than a plant including two or more machines and related equipment circuits. Fewer units of equipment meant less maintenance, and the two down days weekly allowed ample time to repair and, if necessary, to make up lost production. Experience had indicated better sintering quality and rates with larger masses of material, not only on wider machines, but also in deeper beds. The ratio of windbox perimeter to area for the 12x168 ft machine is 0.179, compared to 0.353 for a 6x102 ft machine and 0.617 for a 42 in. x 44 ft machine. This meant less air leakage with resulting fan power savings and less spoilage of charge along the pallet sides. Performance Initial operation of the new sinter plant was made in November 1951 and regular production attained late in December. The average product sinter output during 1952 and the first half of 1953 has been 18.2 tons per hr. The average for one month has been as high as 22.4 tons per hr. Considerable experimenting with varied operating conditions accounts in part for the below capacity — 24 tons per hr — average output, and work to further improve production rate continues. A typical sinter analyses is 66.0 pct Zn, 0.3 pct Pb, 0.1 pct Cd, 0.3 pct S, 8.0 pct Fe, 2.0 pct SiO,, 0.8 pct CaO, and 0.2 pct MgO. Use of this material has made possible increases in furnace burden and improved furnace operation over the former practice using sinter made from Ropp roasted concentrates. Better lead and cadmium elimination in sintering has permitted the furnace production of slab zinc lower in lead and cadmium. Anticipated economies of operation have largely been gained. The sinter plant is operated by seven men per 8 hr shift — one head operator, three equipment operators and three sweepers — plus one oiler on day shift only. While it has been necessary at times to operate seven days a week to produce the required sinter tonnage, the five day work week usually has been adequate. Consumption of natural gas for sinter bed ignition is 200,000 to 300,000 cu ft per day. Green Ore Sintering Practice The 30 to 31 pct sulphur content of the —200 mesh zinc concentrates is the fuel used to sinter the charge, no coal addition being required. In the feed to the machine, sufficient concentrates are added to crushed return sinter fines containing 0.3 to 0.5 pct sulphur to produce a charge averaging 5.0 to 6.5 pct sulphur. Since the return sinter used in Blackwell's practice is varied from — 1/2 to — 1/8 in., the actual sintering mixture of fine sinter and concentrates is somewhat higher in sulphur. The coarser sinter particles are too large to resinter and merely aid porosity in the sinter bed. The ratio of concentrates to return sinter in the charge ranges from about 1:4 to 1:5.5. Variations are based on the appearance of pried up bed sections, bed exit gas temperature trends, windbox suctions, and return sinter size. Sufficient sulphur must be used to obtain fritting of the charge into a soft sinter cake and to aid in the elimination of lead and cadmium. Excessive feed sulphur will result in partial slagging of the cake impairing porosity and prolonging sintering time.

Jan 1, 1954

By Morgan Walker

Intermittent injection of gas in gas-lift pumping is a variation of the common practice in that the gas is delivered to the well for a short period, called the "on time," followed by a period during which none is admitted, called the "off time," instead of being admitted continuously at a constant rate or by intermittent flowing in which it is occasionally delivered to the well in just sufficient quantity to flow off the accumulated head of fluid. The term "gas" is used throughout this discussion but it should be remembered that in so far as the operation is concerned either air or natural gas may be used. The equipment at the well is the same as commonly used in gas-lift installations and gas may be admitted to either the tubing or the casing. It seldom occurs that all the wells on a lease can be pumped economically by intermittent injection from one header. Wells that have flow characteristics which permit their being handled together have their intake lines grouped at a central compressor station. Well groups may consist of two or more wells. The total volume of gas delivered by each group of compressors goes to one well at a time through a quick opening valve, each well connected to the header receiving its charge of gas in turn. Special cases may require a deviation from this arrangement. The distribution of the gas to the different wells is effected by an automatic timing device which operates quick-opening valves on the intake lines. The timing mechanism may be actuated by electricity, liquid or gas pressure, The essential factor in the operation of the timing mechanism is that as one intake valve is closed another must be opened. Water-operated Timing Device Timing devices operate the intake valves either directly, or indirectly by pilot valves. Of the former type one that is operated by water and has given satisfactory service is shown in Fig. 1 and can be made on the lease. The horizontal cylinder is a piece of 10-in. casing about 7 ft. long, closed at each end and free to oscillate about a fulcrum at the center.

Jan 1, 1929

By W. J. Wrazej

THE measurements on the formation of multi-layered scales on pure iron1 and the metal -lographic examination of the produced layer of FeO, Fe,O,, and Fe2O3 shown in micrographs2 throw much interesting light on this apparently well-known subject. Professor Paidassi announced2 that in a few months7 time further results are going to be published with regard to the growth of Fe2O3 and Fe2O3 layers on an Armco iron as a function of temperature. Because of the very thin layers of Fe2O3 which are shown by Paidassi (Fig. 10 of ref. 2) when samples were scaled in air at 700°C for 4 hr and because this is not in agreement with the present author's previous observations, the following experiment was recently carried out. Polished cylindrical samples 13/64 in. in diam and 1/4 in. long from electrolytic iron used for spectro-graphic work (Hilger, H.S. Iron rods, F.693) and an Armco iron sample 1/4 in. in diam of the same length were suspended in a muffle furnace on Nichrome wire and annealed in air for 4 hr at 700°C 5OC. Because of the known easy peeling off of the Fe2O3 layer which is mainly in the form of powder (purple red dust on the surface) the samples were protected against any draft and shock. After annealing, the samples were cooled in air and placed in the mount-

Jan 1, 1954

By L. H. Van Vlack, T. Y. Tien, R. J. Martin

The phase relationships of the MnTe-MnS system were studied by DTA procedures. There is an eutectic at 810°C with about 10 mole pct MnS-90 mole pct MnTe. An eutectoid occurs at about 710°C with approximately 7 mole pct MnS where the MnTe(NaCl) solid solution dissociates on cooling to MnTe(NiAs) and MnS. There is very little solid solubility of MnTe in MnS. ALTHOUGH MnS may exist in three different crystal forms,' only the NaC1-type phase is stable.2 Above 1040°C, MnTe also has the cubic NaC1-type structure. Below that temperature, MnTe changes to the NiAs-type structure.3 This phase transition is rapid for both heating and cooling. As a result the high-temperature crystal form of MnTe cannot be retained at room temperature. Because MnO, MnS, and MnSe are all stable with the NaC1-type structure, and MnTe has this structure at high temperatures,4 solid solution formation could be expected among these compounds. It is interesting to note, however, that a complete series of solid solutions exist only in the MnS-MnSe system,' and that the solid solution is quite limited in the MnO-MnS system.' The MnSe-MnTe system possesses a complete series of solid solutions at high temperatures with separation at lower temperatures.7 Although ion size may be critical in the miscibility of MnO-MnS, it is quite possible that the bond type plays a more important role with the miscibility of MnSe-MnTe. This would permit us to speculate that the miscibility gap would be extensive in the MnTe-MnS system. EXPERIMENTAL Preparation. The samples were prepared by mixing and compacting MnTe and MnS powders. The MnS was previously prepared through the sulfur reduction of Mnso4.8 The MnTe had been prepared by mixing and compacting double vacuum distilled metallic manganese and high-purity tellurium in stoichiometric ratio modified with 1 wt pct excess tellurium. The compacted powders were put in a graphite crucible which was sealed in an evacuated vycor tube. The free space in the vycor tube was made minimal to reduce the loss of tellurium. The sealed assembly was then heated slowly to about 500° C where the free manganese and tellurium reacted vigorously, melting the MnTe which formed. Only one phase, MnTe, was detected by X-ray powder patterns and metallographic techniques. Each compact of MnTe-MnS was placed in a graphite crucible and then sealed in an evacuated vycor tube. The samples were heated at 1250°C for 4 hr and furnace-cooled. Microscopic examination revealed no third phase beyond MnS and MnTe. A typical microstructure is presented in Fig. 1. Identification. X-ray powder patterns were obtained using 114.6 mm Debye-Scherrer camera and Fe-Ka radiation. Mixtures of cubic MnS and hexagonal MnTe were observed in all of the compositions prepared. No lattice parameter change was noticed among different compositions, indicating no solid solution could be retained at room temperatures between these two end-members. A lattice parameter of 5.244Å for MnS was obtained by the Nelson and Riley9 extrapolation method using the diffraction lines of (h2 + k2 + 12) equal 12, 16, 20, and 24. The values, a = 4.145Å and c = 6.708Å, for hexagonal MnTe were obtained from the (006) and (220) lines in the back-reflection region. These values agree well with the values reported by Taylor and Kag1e.10 Differential Thermal Analysis. A differential thermal analysis procedure was used to determine phase relationships since the high-temperature equilibrium conditions could not be retained for examination at room temperature, even when the sealed samples (~0.5 g) were quenched in water. The samples were sealed in an evacuated 4 mm vycor tube with a recess in the bottom to accept a thermocouple. An Al2O3 reference was similarly prepared and the two placed within a piece of insulating fire brick to dampen spurious temperature changes within the furnace. The furnace was controlled by a mechanically driven rheostat which increased the temperature at a rate of about 15°C per min. Known phase changes in the Pb-Sn system1' and the a-to-ß quartz inversion12 were used for calibration

Jan 1, 1969

By E. J. Fasiska, H. Wagenblast

The dilalion of a ivon by interslilial carbon was measured by two independent techniques —dilatometric mesurements at 719 c and X-ray measurments of the urlil cell parameters a1 room temperature after quenching. The relative expansion per increase in cavbon content by both methods is (2.9 + 0.3) x 10-3 pev at. pcl C nrzd is temperature- independent within experimental error. This corresponds to (6.3 5 0.6) cu cm per g-atom for the partial gram-atomic volume of carbon in a iron-only slightly smaller than the atomic volume for iron in the same temperature vange. THE only previous quantitative study of the dilational effect of carbon dissolved in a iron was performed in 1934 by Burns1 which, at the time, generated some discussion of possible sources of experimental error.2 For a system of such widespread importance, we felt that a new investigation was merited. Both X-ray diffraction and dilation measurements were used to determine the expansion of the a iron lattice by dissolved carbon, avoiding as much as possible any previous experimental problems and deficiencies. The dilation method at solution temperature offers not only measurements which are free of residual strain but also, in conjunction with the room-temperature X-ray measurements, a method to detect any large temperature dependence of the partial gram-atomic volume of carbon. To insure that quenching strains did not affect the room-temperature X-ray measurements, wire specimens of constant carbon content but different diameter were examined for such an effect. SPECIMEN PREPARATION The material used for both experimental techniques was "Ferrovac E" iron received in the form of 19-mm-diam rod and stated as having the following impurity contents: C, Cr, Cu, Mn, P, and V, each in the range of 10 to 50 ppm; Co, O, Mo, S, and Si, 60 to 100 ppm; W, 200 ppm; Ni, 230 ppm; N, 4 ppm. The stock material was cold-swaged to 0.71 mm diam for the Debye-Scherrer X-ray camera specimens and portions were cold-rolled from 6.3 mm diam to 0.79- and 0.25-mm sheet for X-ray diffractometer and dilation measurements. The wires were annealed in wet hydrogen for 6 hr at 840°C and 15 hr at 720°C, and then quenched into 0°C water. A chemical analysis for carbon after this treatment gave 0.0046 + 0.0014 at. pct C. Three portions of these wires were subsequently held at 719°C in three different hydrogen + methane mixtures and then quenched, resulting in carbon concentrations of 0.0283, 0.0598, and 0.1067 at. pct C by chemical analysis. After carburizing, the wires were swaged to 0.48 mm and electroplated with silver to prevent carbon loss during subsequent heat treatment. The final heat treatment consisted of holding the wires at 72 1°C for 5 min in a He-2 pct H mixture followed by quenching into 0°C brine. The wires were held at room temperature for a few minutes to remove the silver plating using a phosphoric acid-hydrogen peroxide solution, and then stored in liquid nitrogen until the measurements were made. EXPERIMENTAL TECHNIQUE A) Dilation Measurement. The dilatometer consisted of a gas-atmosphere vertical tube furnace modified so that length changes of a ribbon-shaped specimen could be measured externally. This was done by installing a gas-tight mercury seal at the top of the furnace as shown schematically in Fig. 1. The specimen (21.0 cm long, 1.27 cm wide, and 0.25 mm thick) was suspended in the center of the furnace by 3-mm-diam quartz rods with the upper one passing through the cap of the mercury seal. Above the cap, the upper quartz rod was coupled to a lever exerting a load of about 25 g (-12 lb per sq in.) on the specimen and having a 10 times mechanical magnification. The vertical position of a marker at the other end of the beam was read with a traveling microscope with a precision of 0.01 mm. The temperature gradient of the furnace was meas-

Jan 1, 1968

By H. W. Camp

The past year has had no revolutionary change in the process of petroleum refining, although there have been improvements and developments in practically every phase of operation, due largely, perhaps, to economic pressure. A few years ago, a Mid-Continent skimming plant using 35 gravity crude obtained 28 per cent. gasoline and naphtha; 9 per cent. kerosene, and the remaining yield gave gas oil and fuel oil. Figuring manufacturing cost, but not including sales, transportation, overhead and depreciation, the realization was $1.45 per bbl. of crude. Today, a thoroughly modern and up-to-date skimming plant, having all latest equipment, shows a realization of $1.74 per bbl. on the same basis. Thus it is evident that progressive developments have taken place in the last 2 or 3 years when potential earnings have been increased about 20 per cent. The average refiner is compelled to exert his utmost ingenuity in order to operate with a profitable margin. He has two factors to consider—recovery of maximum yields of profitable oils and the reduction of operating expenses. For the past 8 years, the margin between price of gasoline and cost of crude has grown narrower, constantly. Both these prices are determined by external conditions and not by the refiner himself, but the refiner might have been able to increase that margin had he more carefully controlled his output, limiting his production of light oils to current consumption. Be that as it may, this same economic pressure has given impetus to progress in improvements of primary distillation equipment, including stills, towers and heat-saving devices. A pipe still and bubble cap fractionating equipment can now replace a battery of shell stills, giving better yields, better control, elimination of rerunning and lowering of operating costs. The most recent pipe stills are being equipped either with radiant-heat furnaces or air-preheating systems and improved heat exchange equipment. These can be operated on a fuel consumption as low as 1 per cent. of the charge as compared to a fuel consumption of

Jan 1, 1929

By Grafton Thrasher

For the proper discussion of this subject it is necessary to incorporate in this paper the substance of part of an article published by rite in Metallurgical and Chemical Engineering for January, 1915. CAST-IRON TEST PLUG, SHOWING LOW MOTTLED AND MOTTLED FRACTURES. Several years ago, while I was thief chemist for a malleable-iron company, it occurred to me that the mere regulation of silicon was not sufficient to produce the desired degree of chill. But only after repeatedly encountering this fact in befit open-hearth and air-furnace, as well as cupola metal, was I led to regard variation in the total carbon as the principal cause of disturbance; and I resolved to determine the total carbon as well as the sill on ill every heat, and by a carefully prepared test piece to gauge the approximate degree of chill. The test piece selected was a round plug, 2 in. in diameter and 12 in. long, cast on end

Jan 10, 1915

By M. S. Burton, G. V. Smith, A. Rosen

The kinetics of re crystallization and the effect of recovery on recrystallization of pure iron were investigated within the temperature range of 517" to 632 OC. Grain growth and activation energies were also studied. Two stages can be distinguished during recrystallization; the first is gvowth-controlled and the second is nucleation-controlled. The extent to which the first stage succeeds before the second stage begins depends on both temperature of recrystallization and temperature of recovery. The softening of cold-worked metals and alloys due to transformation of the deformed crystals to strain-free equiaxed grains during annealing is well-known, and early inestiators established that recrystallization kinetics is strongly influenced by minute quantities of impurities. Generally, it is believed that impurities decrease the rate of recrystallization and the rate of grain growth. To understand the basic phenomena of recrystallization, investigations should be on pure materials. Most of the research on high-purity materials has been on metals having the fee Bcc materials, and especially high-purity iron, have been studied only in recent years. It is known that recovery may influence recrystalliation;" however, no general description of the influence, applicable to all materials, has been presented. This paper presents results of a study of the recrystallization kinetics of high-purity iron, after 60 pct cold deformation by drawing, with particular reference to the influence of recovery on the rates of recrystallization and grain growth. From observations of these rates, conclusions are drawn concerning nucleation. MATERIAL AND EXPERIMENTAL PROCEDURE Preparation of Material. High-purity iron, prepared by zone refining of vacuum-melted electroiytic iron at Battelle Memorial Institute under sponsorship of the American Iron and Steel Institute, was used in this study. Table I gives the reported chemical analysis of the material, taken at a point near the last molten zone and thereby rep- resenting the maximum impurity level for the entire bar. Prismatic specimens, approximately 10 x 10 X 50 mm, were sawed from the 50-mm-diam bar, perpendicular to the zone-refining direction, and turned to cylindrical shape. These specimens were sealed in quartz capsules under vacuum, approximately 10"e mm Hg, austenitized at 930° C for 15 min, slowly cooled, removed from the capsules, and cold-worked in air by swaging to approximately 20-pct reduction of area. The encapsulating, austenitizing, and swaging operations were repeated two additional times, after which the samples were encapsulated, austenitized, and cold-drawn to 60-pct reduction of area. A further vacuum anneal at 630°C for 120 min and cold drawing to 60-pct reduction of area produced wire 2.8 mm in diameter. The drawn wire was electropolished to remove deformed material on the surface, after which it was sawed into 4-mm-long specimens for the recrystallization study. Microscopical examination before the final cold reduction revealed equiaxed grain structure with very fine grains in a thin layer near the surfaces of the specimen and nearly uniform ASTM 3-4 grain size in the center. Recrystallization Heat Treatment. a) Direct Recrystallization of Cold-Worked The 60 pct cold drawn iron specimens were recrystallized at five temperatures, 517, 556, 590°, 612, and 632C, in a lead bath covered with graphite (the temperature was controlled to 1°C). Specimens were treated for twelve different times at each temperature, and all were water-quenched after heat &eatment. b) Recrystallization Following Preliminary Recovery Heat Treatment. After cold working, specimens were sealed into quartz capsules under vacuum, 105 mm Hg, and recovery-annealed at 362", 400", and 440°C for 20 hr prior to recrystallization. No evidence of recrystallization was found

Jan 1, 1964

By A. R. Troiano, E. A. Steigerwald, F. W. Schaller

The kinetics of crack propagation in a hydrogenated high-strength steel at subzero temperatures indicated that cracking progressed in a discontinuous fashion. The delayed failure process thus involves a series of crack initiations rather than the continuous growth of a single crack. The incubation time required for the initiation of delayed failure was controlled by the diffusion of hydrogen. The activation energy for the process was 9120 cal per g-alom. As the test temperature was lowered the incubation time constituted a greater percentage of the total tinze to fracture, and al -50°F the incubation and fracture times were essentially coincident resulting in instantaneous, catastroplzic fracture. A unique feature of hydrogen embrittlement is the delayed failure process in which the material fails under the action of a sustained load even though it is capable of supporting a higher load for a finite period of time.')' Delayed failure of steel and titanium is characterized by an incubation time, preceding the initiation of a crack in a highly localized region, and the subsequent growth of the crack to ultimate failure.3-5 The kinetics of crack growth in hydro-genated high-strength steels have been studied through the use of resistance measurements and have an important bearing on the mechanism of delayed failure. Delayed failure is believed to be merely a facet of hydrogen embrittlement in which sufficient time is allowed during a test for hydrogen diffusion. The current theories employed to explain hydrogen em-brittlement can be grouped into two types. one6-8 explains the embrittlement on the basis of the pressure exerted by molecular hdrogen in lattice voids or defects while the other9-10 attributes the embrittlement to the influence of hydrogen in the lattice. The mechanism used to explain the nature of the crack kinetics in delayed failure is based on the stress-induced diffusion of hydrogen to the area of maximum triaxiality.3 When the hydrogen concentration in this region reaches a critical value, a crack is nucleated. This initial crack propagates instantaneously until stopped by the higher fracture stress of the adjacent material of lower hydrogen content. The continuation of cracking must then await the further diffusion of hydrogen to the new region of triaxiality near the base of the crack where another initiation will occur. From this mechanism it follows that crack propagation is nothing more or less than a series of initiations with limited fracture. The purpose of this investigation was to examine the kinetics of crack growth in an effort to determine whether or not the process was discontinuous. Studies of crack propagation were conducted at low temperatures to retard the diffusion of hydrogen which is presumed to be the rate controlling process in delayed failure. MATERIALS AND PROCEDURE Specimen Preparation—A commercial heat of air-craft quality SAE-AISI 4340 steel, designated as Heat G, was furnished by the Republic Steel Co. in the form of %-in. hot-rolled bars. The material had the following chemical analysis: Composition of 4340 Steel—G Heat C Mn Si Ni Cr Mo 0,395pct 0.82pct 0.29pct 1.76pct 0.85pct 0.25pct Notched tensile specimens with less than a 0.001 in. radius, Fig. 1, were used throughout the investigation. The specimens were heat treated to a 230,000 psi strength level according to the following sequence: a) Normalize bar stock at 1650°F for 1 hr, b) Stress relieve at 1200°F for 4 hr and furnace cool,

Jan 1, 1960

THE Institute met on Wednesday evening, May 22d, in the parlor of the Stanton House, Dr. T. Sterry Hunt, President, in the chair. The President delivered an introductory address on the Brown Hematite Deposits of the Great Valley, after which the following papers were read and discussed : Note on the Result of an Experiment with the Wheeler Process of Combining Iron and Steel in the Head of a Rail, by W. E. C. Coxe, of Reading, Pa. On the Jenks Corundum Mine, Macon County, N. C., by Dr. R. W. Raymond, of New York City. On Wednesday afternoon, previous to the opening session, the members who had already arrived in Chattanooga, were taken by the Local Committee to the works of the Roane Iron Company, and Chattanooga Iron Company, and then to the top of Lookout Mountain, where, at the request of the members present, Dr. Hunt described the geological and geographical features of the Chattanooga region, with the magnificent panorama spread out before them as a map. On Thursday morning an excursion was made by steamboat down the Tennessee River as far as Shellmound. Here cars were taken to the coal mines of the Dade Coal Company, where the members were courteously received by Mr. E. B. Wells, the Superintendent. After a trip through the mines the party partook of a collation provided by the company. South Pittsburgh, on the Tennessee River, was next visited, where the Southern States Coal, Iron and Land Company have a large blast-furnace plant in the course of erection. After conducting the party through the works, shops, etc., Mr. James Bowron, the manager, entertained the members with graceful hospitality at dinner. The second session was held on Thursday evening for the transaction of business. The President, Dr. T. Sterry Hunt, appointed Messrs. W. E. C. Coxe, R. H. Richards, and F. J. Slade, scrutineers, to examine the ballots for officers for the ensuing year.

Jan 1, 1879

By A. E. Perkins

fractured ingot will show a complete diagonal structure. If the temperature is lowered, the equi-axed zone is larger and the pine tree growth is less. A small ingot, though, is prone to this columnar structure, even though the casting temperature is kept down. The speed of cooling after solidification is slower in the hollow ingot than in the solid, therefore the granulation, which takes place after the crystals have formed from the liquid metal, is apt to produce larger grains than in the solid ingot. This is not a detriment. The original crystal size is of much more importance. The size of the grains due to this granulation constantly varies in response to mechanical work and subsequent heat treatment. Surface weakness, as shown by seaming and checking on the exterior when working or by cracking in hardening, is in some measure the result of the surface stresses of the ingot when cast. The temperature of the ingot mold or speed of freezing of the exterior of the ingot is of great importance and much seamy and cracked steel is caused by a too quickly cooled skin. Ingots that are turned or milled all over will not seam very much in working, in fact they are practically free from seams, whereas an ingot rolled without a preliminary machining operation is full of seams and cracks, some long and some short. It has been said that these short seams and cracks in the surface of the bar are the result of elongated depressions in the surface of the ingot and that if an ingot is cast very smooth it should give fewer surface defects. This is partly true, but an ingot cast very hot and having a very smooth skin will crack and seam very badly in the mill, as will the surface of an ingot poured very cold, which is very crinkly, because of the low temperature of the metal. The cause of the cracks and seams in one is not the cause of the cracks and seams in the other. The tube method of hollow drill steel manufacture is superior to the older method because of: (1) Greater freedom from external and internal straining; (2) the inherent small crystal size; (3) absence of harmful segregation, resulting in weakness of wall of hole. (4) less liability for steel to crack in inside of hole during forging or hardening; (5) toughening effect, arising from mild steel wall of hole limiting the intense hardening on quenching. Breakage and Heat Treatment or Rock-drill Steel By A. E. Perkins, Pittsburgh, Pa. Actual figures showing the superiority of one section or another are difficult to obtain. In a given size of steel, however, the cruciform sec -tion shows the most breakage; it is inherently a weak section. It contains less steel per foot than any other standard section of the same size and when rolled the wings tend to cool off setting up cooling stresses.

Jan 1, 1922

By G. A. Vissac, R. G. Minet, N. E. Sylvander

R. G. Minet—The authors' description of the remarkable progress made in the last few years in applying the fluidized solids technique to the problem of lignite drying and carbonization clearly demonstrates that engineering techniques available today may make many processes practical and profitable which a few years ago were considered otherwise. As pointed out in the article, the future of the carbonization step hinges on the value and utilization of low temperature tar. On paper, at any rate, this tar looks like a valuable raw material for the chemical industry to use. Some 50 to 60 pct may be converted to pitch for electrodes, roofing, road tars, and other valuable products; the 25 to 30 pct tar acids could conceivably form a basis for a new low cost resin or plastic of the phenolformalde-hyde type. Yet these materials are so new and dissimilar from available sources that much work must be undertaken by the chemical industry before they will be accepted. Now that the work of Dr. Perry and his colleagues has made a large supply of low temperature tar a real possibility, I would expect the chemical industry to accelerate its work in this field. On the basis of certain data available in the literature it appears possible to produce a more aromatic tar, although in smaller yield, by operating at temperatures in the range of 1300" to 1500°F. Operating a fluidized bed process for lignite at these conditions should be technically possible, at least, and could produce a tar having more familiar characteristics. I wonder if Dr. Parry would care to comment on such a possibility. Incidentally, in our own work on carbonizing coking coals in fluidized beds, using Ohio, Pennsylvania, and West Virginia high volatile bituminous coals, we have obtained yields which agree with the correlation given for tar yields vs moisture and ash-free volatile Btu. Our data are slightly under the line, but certainly in the range of the correlation. We have also obtained evidence in support of the authors' statement as to the effect of air on the process. In our pilot plant all the heat required for carbonizing is released by internal combustion of char in the fluidized bed in normal operation. We are also equipped to obtain all carbonization heat by external electric heaters on the shell of the carbonizer while introducing only an inert gas to the process. We note no difference in tar yield or characteristics between the two operations. In the case of the gas, however, it appears that some hydrogen is consumed by the air combustion. We would be interested in hearing in a little more detail about the hot dust and char handling problems at Sandow. Have the authors found char subject to spontaneous combustion? Have they ever tried a coking coal in their pilot plant? V. F. Parry (author's reply)—Production of a more aromatic tar by operation of the carbonizer at 1300" to 1500°F does not appear to be economical. 1) The capacity of a reactor operating at 1500°F would be 30 to 50 pct less than the capacity at 932 °F and the cost of processing would increase materially. 2) The cracking of tar vapors in a reactor requires appreciable time to complete the reactions and it is doubtful that considering the very short time of residence of tar vapors within the reactor (4 to 10 sec after evolution) the basic character of the tar would be changed significantly. This is indicated from the data reported in Table XIV. 3) General studies have shown that it is advisable to operate at the minimum temperature to produce the maximum tar and minimum gas. 4) Operating problems and the maintenance of vessels and reactors, and the hazards of handling hot char, increase with the temperature of carbonization. It is technically possible to operate at temperatures as high as 1500°F, but in my opinion it is not economical or desirable. We believe that the primary tar must be won in the simplest way and then processed alone to change its character for production of desired products. It is interesting to have confirmation of our observations on the reaction of air with the products of carbonization. The major reaction is with the char, fol-

Jan 1, 1957

The following communication has just reached the Institute, from the office of the Provincial Geologist, Department of Lands,-Forests and Mines, Ontario, Canada: During the autumn of 1917 gold was discovered in unsurveyed territory south of Lake Abitibi in northeastern Ontario. This area lies about 70 miles almost directly east of the well known Porcupine area. During the coming summer, the Ontario Bureau of Mines is to make a geological survey of this new gold area. Following the custom of Ontario, this area is being divided into townships, 6 miles square. These townships have recently been given the following names in honor of men well known in the mining and geological world. In alphabetical order the names are as follows: Frecheville-Prof. Wm. Frecheville, Professor of Mining in the Royal School of Mines, London; Past President of the Institution of Mining and Metallurgy. Garrison-Mr. F. Lynwood Garrison, Mining Engineer, Philadelphia, Pa. Harker-Dr. Alfred Harker, F. R. S., immediate Past President of the Geological Society of London.

Jan 6, 1918

By H. N. Mead

In a reservoir when gas comes out of solution and rises, additional pressure is created because of the change in position of this gar in the bounded volume. If this pressure effect is not taken into account as a pseudo-influx ill mate rial balance calculations on reservoirs in which there is evolving gas, an error is introduced that is directly proportional to the length of oil column and amount of gas evolved and inversely proportional to the reservoir pressure. In reservoirs with small oil column this pseudo-influx is of little importance. The larger the oil column the more important the effect becomes. The most important application, however, will be for reservoirs with declining pressure in which increasing water entry has been indicated by material balance calculations. It could be that this indication is the result of the cited pseudo-influx and not water entry at all. This paper attempts to explain this phenomenon in relation to material balance calculations and prevents an approximate method of determining tile pseudo-influx. INTRODUCTION Only recently has the pressure-volume relationship of gas rising in a liquid appeared in engineering literature, although its effect has been discussed for several years—especially among engineers engaged in drilling operations. The writer published a paper in 1957 in which this phenomenon was examined in relation to blowouts in drilling wells.' Also, in 1957 Stegemeier and Matthews' authored a paper in which the relationship was presented with respect to pressure build-up tests when shutting in producing wells. In this paper the effect will be called "pressure inversion" which is descriptive of the phenomenon. Fundamentally, the effect just mentioned is the result of changing the position of a quantity of energy contained within the gas itself (as a result of its compression) within the bounded volume in which the gas exists. If the gas were allowed to expand "beyond all bounds" there could be no pressure inversion effect. This is because all of the energy contained within the gas as a result of compression would have been re- PRESSURE INVERSION A phase that has not been discussed in the literature is the effect of pressure inversion upon material balance calculations in reservoirs in which the reservoir pressure drops with reservoir withdrawal and is below the bubble point. This action releases solution gas which, after the critical gas saturation has been reached, will tend to rise and collect at the top of the reservoir. The pseudo-influx caused by this effect could be great enough in reservoirs of large oil column and high permeability to render invalid any analyzer studies made on them — if pressure inversion has not been taken into account. Most suspect would be those reservoirs with large oil column in which increasing water entry has been predicted but the bottom wells have not yet produced water. Example 1 Simply stated, this phenomenon exists in oil reservoirs because of the difference in density and expansibility between gas and oil. For example, if a bubble of gas exists at the bottom of a 1,000-ft column of oil having a gradient of 0.30 psi/ft with the pressure at the top of the column zero, the bubble of gas will be compressed to a pressure of 300 psi. If temperature and the combined volume of the oil column and the gas bubble remain constant, as the gas bubble rises in the oil column it will have the same volume and consequently the same pressure at any point. Under these conditions when thc bubble reaches the top of the oil column, the pressure will be approximately 300 psi at the surface and approximately 600 psi at the bottom of the oil column. If it is assumed that the oil is incompressible the pressures will be exactly 300 and 600 psi, respectively.

By H. E. Criner, M. G. Driessen

Maurice Rey—The influence of cyclone diameter upon the fineness of separation is an important point which, however, cannot be discussed adequately if the injection pressure or the rate of flow are not specified. Perhaps some light can be thrown on the matter by using the formulas derived by Dahlstrom. Let us consider several geometrically similar cyclones where the apertures e and b are equal and proportional to the diameter D and which are operated with the same pressure drop. Eq 8 of Dahlstrom's paper can be written: Q Q = K D'. " or. if F is constant: Q = K D18 K is a constant of proportionality. Introducing this value of Q in eq 13 gives elimination efficiency = K D ,41 Elimination efficiency, in the terminology of Dahl-strom, means the diameter of particles, in microns, which divide equally between the underflow and the overflow. This denomination is regrettable and it would be preferable to call it diameter of separation or characteristic size or any other name connoting a size rather than an efficiency. Whatever the name used, the above equation shows a slow increase in the fineness of separation when the diameter of the cyclone decreases. For example, if a 14-in. cyclone gives a 400-mesh separation (37 microns), geometrically similar cyclones, having the same pressure drop will give separations at the sizes shown below.

Jan 1, 1951

By M. G. Driessen, H. E. Criner

Maurice Rey—The influence of cyclone diameter upon the fineness of separation is an important point which, however, cannot be discussed adequately if the injection pressure or the rate of flow are not specified. Perhaps some light can be thrown on the matter by using the formulas derived by Dahlstrom. Let us consider several geometrically similar cyclones where the apertures e and b are equal and proportional to the diameter D and which are operated with the same pressure drop. Eq 8 of Dahlstrom's paper can be written: Q Q = K D'. " or. if F is constant: Q = K D18 K is a constant of proportionality. Introducing this value of Q in eq 13 gives elimination efficiency = K D ,41 Elimination efficiency, in the terminology of Dahl-strom, means the diameter of particles, in microns, which divide equally between the underflow and the overflow. This denomination is regrettable and it would be preferable to call it diameter of separation or characteristic size or any other name connoting a size rather than an efficiency. Whatever the name used, the above equation shows a slow increase in the fineness of separation when the diameter of the cyclone decreases. For example, if a 14-in. cyclone gives a 400-mesh separation (37 microns), geometrically similar cyclones, having the same pressure drop will give separations at the sizes shown below.

Jan 1, 1951

By Frederic Benard

PRIoR to 1936, the Ontario Refining Co. received all incoming blister copper from The International Nickel Company's smelter in the usual form of 460-lb. cakes, or slabs. These were received in open cars in lots of 250 pieces. At the refinery the cakes were unloaded onto narrow- • gauge cars, for convenient handling and pickup by charging cranes. In March 1936, an investigation was started on the feasibility of transferring converter copper in the molten state from the smelter to the refinery anode furnaces, a distance of 1 1/4 miles. Although common in steel practice, the transportation of blister copper in this form had not previoisly been attempted and a preliminary study of the various factors involved was therefore necessary. For this purpose, a series of experiments was made in which molten copper, removed at different stages during the furnace cycle, was held in a small portable holding furnace. This vessel was essentially a refractory-lined steel cylinder provided with ports for filling and emptying, heated by an oil burner. Dimensions of the steel shell were 3 ft. 10 in. diameter by 7 ft. 3 in. long, and thickness of refractories depended on the design and combination used for the particular experiment. The vessel was filled with approximately 2 1/2 tons of copper at a predetermined temperature, the lining having been preheated to a definite point by means of an oil burner. All openings were well luted and temperature readings were made every 15 min. by means of an immersion-type thermocouple. In this manner the rate of heat loss resulting with different refractory design could be developed. The ratio of exterior surface to weight of metal was taken into consideration in comparing the experimental results with what might be expected for a full-sized unit, and observations were also made on type and degree of slag accretion. It was not possible to get as much information on this latter point as desirable, but all evidence showed that the problem would be control of slag build-up rather than attack on refractories. From the information derived, and in consultation with the engineering staff of the supplying company, an order was placed for the first

Jan 1, 1944

By AIME AIME

THE No. 9 mine of the Wheeling & Lake Erie Coal Mining Co., a subsidiary of M. A. Hanna & Co., at Fairpoint, Ohio, has normally produced about 1000 tons of coal daily for several years, but recently it was converted into an experimental mine to afford means of studying new methods and equipment under consideration for development and mining. Among other projects, the possibility of using a duck-bill, self- loading conveyor in driving entries, with a view of in- creasing the rate of progress where quick development is of importance was studied. Actual operation soon revealed that even though break-throughs are made ,every 60 ft., as required by the state mining laws, the :amount of natural Ventilation reaching the working face was not sufficient to supply the men and that in ,order to obtain a plentiful supply of pure. air and maximum efficiency and to avoid costly interruptions after shots, it was necessary to supply auxiliary ventilation by using Ventube and a Vano fan.

Jan 1, 1929

By W. David Menzie

An inventory of the mineral resources of a region is a most desirable basis for planning their systematic development. In the absence of appropriate samples upon which to base a reliable estimate of this inventory, investigators have resorted to a number of indirect approaches; the unit regional value concept forms the basis for one such approach. The produced resources of a region are a function of the inventory multiplied by the degree of intensity (some fraction between zero and one) of development of the resources. A convenient means of expressing this amount is to accumulate the weight and value of resource and to prorate the totals over the area represented by the unit sampled; i.e., weight and value per unit area or tonnes/km.2 and U.S. 1967 $/km.2. When this approach is used for the U.S.A., South Africa and Rhodesia the average value of (log.) U.S. 67$/km.2 for the states of the U.S.A. and South Africa are similar ($55,176 U.S.$67/km.2 and $52,538/km.2 respectively); whereas, Rhodesia is relatively underdeveloped (10,301 U.S.67$/km.2). On the other hand if the individual commodities are used as a basis for comparison, the U.S.A. shows the greatest diversity (67 commodities out of a possible total of 75) with South Africa next (50 commodities) and Rhodesia last with only 26 commodities. Since it is known that area and value are not simply related perhaps diversity is directly related to area. Again the kinds of commodities which have contributed the greatest value to the totals differs, with fuels (petroleum, coal and natural gas) predominating in the U.S.A. totals; whereas, South Africa and Rhodesia obtain their greatest contributions from gold, diamonds (S. Africa) coal and asbestos. In each case the greatest value of resources is produced from sedimentary rocks. As a somewhat different kind of example, consider a single resource (petroleum, the most valuable in the U.S.A.) over a large area (number of sampling units) the U.S.A. by state. Furthermore, assume that the model frequency distribution of the amount of petroleum (tonnes/km.2) is log normal. Then the present production fails to match the model first because 17 states (34% out of 50) have not produced petroleum. Of the remaining 33 states, Louisiana has produced the most (15,177 tonnes/km.2) and the frequency histogram is still skew. A spatial analysis of the distribution of the amount of petroleum by state shows that the samples (i.e., states) are not random; the non-producers and producers tend to cluster. It remains to be seen if this is indeed a true representation of the incidence of petroleum or is a function of the exploration philosophy currently in vogue.

Jan 1, 1977