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

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

Jan 1, 1962

By A. Mitchell

An approximate phase diagram has been developed for the CaF2-CaC2 system, indicating a eutectic point at 1240°C, Ncac2 = 0.13, and no detectable solid solution in either phase. The liquidus line is shown to correspond to a simple c22- ion in solution. A thermo-chemical study of&apos; the reaction between carbon-saturated Ni-Ca alloys and CaC2-CaF2 liquids indicates that lhe Raoullian activity coefficient of CaC2 in dilute solution in Cap2 al 1500°C lies between 8 and 10. Some effects of the stabilily of Cap2-CaC2 solutions at high temperatures on electroslag remelting praclice are outlined. THE alkaline earth acetylides. MIIC2, have a reasonably high thermochemical stability at high temperature in the solid state,&apos; with the exception of magnesium, which forms an unstable acetylide at low temperatures (-500°C) and a carbide, Mg2C3, in the range 700&apos; to 1000°C. The acetylides of calcium and barium have been shown to have limited solubility in their respective chlorides,&apos; and further these solutions contain the acetylide as a C: ion.&apos; The equivalent magnesium solutions have not been studied. Although calcium "carbide" is used as a desulfuriz-ing reagent in steelmaking. and is possibly present as an acetylide-oxide phase in very basic electric arc practice slags, the acetylide ion appears to be substantially unstable in a silicate slag.* As a conse- *This instability arises from equilibria in the reaction: CaC2 + CO = (Ca0) + 3C where the low intrinsic solubility of CaC2 in silicate lattice, and the low activity of CaO in a silicate solution where CaO/Si02 < 1, combine to give a very small equilibrium concentration of CaC2 in solution in such silicate slags at temperatures in the region of I 500°c, even under carbon-saturated conditions. Under highly basic conditions, a liquid CaO-CaC2 phase may separate from the silicate system quence of this, the possibility that reactions involving CaC2 in silicate solutions are of importance to general steelmaking practice is remote. However, in operations involving a slag primarily based on a halide, or alkaline earth oxide, we must take into account the possibility that CaC2 will appear in quantities sufficient to significantly affect both the chemical and physical properties of the slag. The work outlined below presents a study of the CaF2-CaC2 system intended to provide sufficient data to allow an estimate of the importance of this system to electroslag remelting and welding practice. However, we should indicate at this point that there will be other processes, e.g., heat treatment, flux cleaning of castings, fused salt electrolysis, and so forth, where alkaline-earth halide fluxes are in contact with carbon, graphite, or carbides, and where halide-acetylide solutions must be taken into account. EXPERIMENTAL 1) Structural Studies. In view of the difficulty ex-perienced in handling CaC2 prepared from calcium turnings and propane gas at 700°C, it was decided to use solutions prepared directly in the equilibration apparatus, Fig. 1. The starting materials were: a) Ni-Ca-C alloy, prepared by adding calcium to liquid nickel held under calcium fluoride in an induction-heated graphite crucible; b) calcium fluoride, prepared by fusing calcium fluoride powder (British Drug House "EXTRA PURE") calcium fluoride in an induction-heated graphite crucible, in air, followed by electrolysis between graphite electrodes at 1 amp cm-2 density, for 10&apos; coulombs per g CaF2. This procedure decomposes the CaO produced by hydrolysis during the fusion step, replacing it by CaC2; Ca2+ + 2e-Ca*(l) Ca*(l) + 2C(gr)-(CaC2)caF2 O2- -2e-O*(g) O*(g) +C(gr)-CO(g) This results in a composition of between 2 and 5 wt pct CaC2 in CaF2. Fifty grams (in lumps) of this material were placed in a graphite crucible, together with Ni-Ca-C alloy (averaging 20 wt pct Ca), and the equilibration apparatus assembled. The alloy reacted with the crucible at high temperature to give CaC2, which dissolved in the calcium fluoride solution to give the desired composition. Cooling curves were plotted manually for these liquids, with rapid stirring and CaF2 seeding to minimize supercooling, and using a Pt/Pt 13 Rh thermocouple calibrated on the freezing points of nickel and copper. This gave a reproducibility of ±0.l°C. and an absolute accuracy of the thermocouple of ±l°C. An example curve is shown in Fig. 2, with the CaF2 end of the binary system in Fig. 3. The CaF2-CaC2 ingots were crushed, under dry nitrogen, and sampled for chemical analysis and X-ray examination. Analytical details are given in the Appendix. Powder diffraction data indicated that the only phases present in all samples examined were calcium fluoride and tetragonal (Types I and 111) calcium acetylide,4 with no evidence of solid solutions or compound formation. 2) Thermochemical Studies. The apparatus used to obtain activity data on CaC2 in these systems is shown in Fig. 4. It consists of an arrangement whereby the graphite crucible and its contents (CaF2-CaC2. Ni-Ca-C) can be rapidly cooled without exposure to air. Trial experiments to determine an equilibration time by ap-

Jan 1, 1969

By A. L. Wilder, S. N. Dixon

Introduction Coeur d&apos;Alene Mines Corp.&apos;s largest precious metals property is located in the historic Rochester Mining District 40 km (25 miles) northeast of Lovelock, NV. The property encountered cold weather operational problems soon after its fall start-up in 1986 due to its elevation of over 1830 m (6000 ft). The problem of ice buildup on the heaps because of sprayed solution application was faced immediately. It was felt that allowing ice to build up all winter long until a spring thaw was impractical due to the large area under leach. Further, the operating cost and delivery schedule for a solution heating system was unacceptable. The development and installation of a leach solution distribution system using drip emitters made efficient, cost-effective winter operation possible. Other benefits of this system have also been observed and are discussed here. General process description 15,422 kt/day (17,000 stpd) of - 1.27-cm (-1 /2-in) crushed ore from the three-stage crushing plant are delivered to the leach pad using 77.1 t (85 st) rear dump haul trucks. The ore is drifted into place with a D-9 bulldozer. Leach panels are contiguous and are approximately 8861 m&apos;(90,000 square ft) in area built in 6-m (20-ft) lifts. New panels are built on top of older areas to a final height of 61 m (200 ft). Each panel is ripped and cross-ripped prior to leaching. Barren solution is distributed to the heap using drip emitters at rates of 0.02 to 0.41 L/min/m2 (0.0005 to 0.01 gpm per sq ft), depending on the age of the panels. The pH of the leach solution is 10.7 with a cyanide concentration of 0.75 kg/t (1.5 lb per st). Approximately 50% of the silver and 80% of the gold are finally recovered. Pregnant solution percolates though the heap and flows by gravity into one of two 9.46 ML (2.5 million gal) pregnant solution ponds. The solution is then pumped to a conventional Merrill-Crowe process plant. Clarification takes place in three 9464 L/min (2,500 gpm) capacity filters. The solution is then pumped to a packed vacuum deareation tower for the removal of dissolved oxygen. Typical deareated solution contains 0.7 parts per million dissolved oxygen. Precipitation of gold and silver is accomplished by adding a zinc dust slurry to the deareated solution at the suction of the filter press feed pump. Precipitated gold and silver are recovered in three recessed plate and frame filter presses. Barren solution is discharged into a 11.7 ML (3.1 million gal) pond where cyanide makeup occurs. This solution is pumped back to the heap for further leaching. The precipitate filter cake, containing approximately 75% dore (Ag + Au), is then fluxed with anhydrous borax, soda ash, sodium nitrate and fluorspar to yield a neutral, bisilicate slag. The fluxed precipitate is then charged into a propane-fired melting furnace and heated to 1150° C (2100° F) for 3 1/2 hours. Slag and dore bullion are poured into conical cast iron pots yielding buttons of 800 to 1000 troy oz. The dore typically contains 98.5% silver and 1 % gold. Slag is crushed and tabled to recover the trapped dore blebs and beads. Concentrate from the table is returned to the furnace. Table tails are sent to the crushing circuit and out to the leach pad. Solution application The area kept under leach at Rochester is approximately 130 000 m2 (1.4 million sq ft). Barren solution is delivered to the pad at 21.2 kL/min (5600 gpm) for a resultant application rate of 0.16 L/min/m2 (0.004 gpm per sq ft). A traditional solution sprinkling system using No. 12 Senninger Wobblers with individual pressure regulators was installed at the onset of leaching activities. The Wobblers were placed at 9.1-m (30¬ft) staggered centers and were fed off of a gridwork of Yellowmine plastic piping. Solution flow rates were moni¬tored to each panel. The onset of cold weather with an average nighttime temperature of -12° C (10° F) made it apparent that continual operation would not be possible with the sprinklers. A significant amount of ice was built up on top of the heap, making maintenance and pipe removal dangerous, if not impossible. Leach solution application was restricted to daylight hours to inhibit ice formation. Process plant flow rates were reduced to maintain steady-state operating conditions. However, as daylight temperatures dropped below freezing, ice continued to accumulate due to the sprays. Besides the obvious operating hazards brought on by the growing icefield, there was also the potential environmental hazard associated with an early thaw melting the ice too rapidly for the solution containment facilities. One other option for preventing ice formation was heating of the barren solution prior to spraying. Initial plant design allowed for expansion of the propane storage and distribution system as well as modification of the barren piping for a solution heater. This option was not exercised because the operating costs for an adequate system would have been prohibitive, and timely delivery of a system was not available. An investigation was conducted on the various drip irriga¬tion products available, since subsurface solution applicators would eliminate ice formation altogether. Systems utilizing external flow emitters were ruled out because of their ten¬dency to clog when buried. Emitter systems using perforated tubing were also eliminated from consideration due to their inability to adequately control flow over required lengths of tubing. An in-line emitter system was finally selected which demonstrated clog resistance and adequate flow control, enabling direct burial.

Jan 1, 1990

By R. W. Gurry

In a series of charts this paper presents the composition of all gas mixtures, composed of the elements carbon, hydrogen, oxygen and nitrogen, which at temperatures from 1000° to 1800°F are in equilibrium with (1) austenite of various carbon contents, (2) iron and iron carbide, (3) graphite, (4) iron and its oxide. THIS paper presents the results of calculations made to determine the proportions of CO, CO2, CH4, H2, H2O and N2 in gas mixtures which, at temperatures from 1000" to 1800°F, satisfy, individually, the following conditions: (1) equilibrium with carbon steel of specified carbon content throughout the stable 7 iron region; (2) equilibrium with iron and iron carbide, both above and below the eutectoid temperature; (3) equilibrium with graphite; (4) equilibrium with iron and its oxide. From these data a new type of chart has been prepared which permits one to determine, from a room-temperature analysis of the furnace gas in question, the effect of the gas upon the steel at furnace temperature. Thus a guide is provided as to the carbon content which will result and as to the possibility of oxidation or sooting. All of the atmospheres commonly used in the commercial heat treatment of steel are composed of some or all of the simple constituents CO, CO2, CH4, H2, H2O and N2, and also in some cases oxygen or higher hydrocarbons. As the gas mixture is heated certain alterations in the proportions of the constituents take place, and at the temperature of the furnace the composition is, in general, not at all that of the entering gas. If equilibrium in the gas phase is presumed a calculation involving the use of certain fundamental data predicts for a certain temperature the carburizing, decarburizing, or sooting characteristics of a given atmosphere, and, upon the additional assumption of equilibrium between gas and metal, also the oxidizing ability of the gas and the ultimate carbon content of the steel. The extent to which these predictions are fulfilled will depend upon how closely the assumptions of equilibrium are realized in any particular case. Although at lower temperatures equilibrium is often not reached, there is considerable evidence indicating that above about 1000°F the approach to equilibrium in the gas phase is generally substantially complete, particularly in the vicinity of the steel which acts as a powerful catalyst in promoting reactions in the gas phase. The extent of the gas-metal reactions is commonly affected essentially by the sojourn at temperature; equilibrium with respect to carbon, for example, is accomplished simply by continuing the treatment long enough. However close the approximation of equilibrium may be in any instance, the above mentioned calculation indicates the condition of the steel at equilibrium, and at the present time this is the only basis of control of a furnace atmosphere. The effect at elevated temperature of a gas of a certain composition at room temperature upon a given steel has customarily been judged by first calculating from gas equilibrium constants the proportions of the gas constituents at the temperature of the steel, then comparing certain of these with the proportions known to be in carbon or oxygen equilibrium. This process is tedious and time-consuming, in particular because the calculation generally involves a series of successive approximations; and since some knowledge and familiarity with this type of computation are required, not everyone needing the information has been, in the past, in a position to obtain it. By making a series of equilibrium calculations, combining with fundamental data for gas-metal reactions, and plotting the results in a special way, a chart has been prepared which enables anyone

Jan 1, 1951

By J. C. Trantham, J. W. Marx

From 1955 to 1958 the Phillips Petroleum Co. conducted a series of small scale counterflow combustion field tests in a tar sand about 60-ft deep and 6 to 12-ft thick near Bellamy, Mo. A total of seven different well patterns, including conventional five-spots and seven-spots plus a 15-well line drive pattern and a 10-well radial pattern, were employed. Electric heaters, gas burners and wellbore fuel packs were tested as counterflow ignition devices. Direct drive ignition followed by reversal to counterflow operation was not possible in this case because of formation plugging by the semi-solid tar during the direct drive phase. Sustained counterflow burning was achieved with wellbore fuel packs under conirolled conditions which permitted close correlation of fire front velocity, air velocity, air-oil ratios and yields for a wide variation in process parameters. The tar in place was about 10&apos; APl with a reservoir viscosity greater than 500,000 cp. The composite oil prodlcct was 26&apos; API with a viscosity in the range of 5 to 15 cp. Vertical sweep efficiency in the line drive pattern was essentially 100 per cent, with no evidence of gravity segregation. Original tar in place ranged between 800 and 1,000 bbllacre-ft, specific rock permeability averaged about 800 md before burning and effective air pemeability with residual oil and water in place (at the time of ignition) averaged 250 md. The volume of oil recovered during stabilized line drive counterflow burning represented about 67 per cent of the volume of tar originally in place in the burned out zones. A minimum was found when air-oil ratios were plotted against formation air velocities, and a limiting air velocity existed below which the counterflow fire front reversed and burned back over its own trajectory, using the residual coke left behind. INTRODUCTION Early in 1955 the Phillips Petroleum Co. began preparations to field test counterflow underground combustion as a method for producing oil from high viscosity hydrocarbon deposits, such as bituminous (tar) sands. At that time all published information on the use of underground burning io increase oil recovery was based on the direct drive process, in which the fire front moved through the formatim in the same direction as the injected air stream. Such direct burning is not applicable to many heavy oil sands or to most tar sands because the heat-thinned native hydrocarbon congeals in the cold rock ahead of the fire front forming a gas permeability block which smothers the combustion. Laboratory experiments first demonstrated that this permeability blocking would not occur if the fire front and the air stream moved in opposite directions. In this counterflow (reverse) burning process the heated heavy oil or tar is driven back through the combustion zone. Here thermal cracking produces relatively light hydrocarbon products which pass through the heated rock behind the fire front (largely in the vapor phase) and are incapable of causing a gas permeability block.&apos; Exploratory wring revealed that consolidated bituminous sandstones with a combination of tar saturation, permeability, thickness and depth favorable for experimental field testing existed at several points in western Missouri. By the fall of 1955, a test site for determining technical feasibility of the counterflow process under field conditions had been selected near Bellamy, Vernon County, Mo. — about fifty miles north of Joplin. The pay zone was too thin and too shallow to constitute a commercial prospect, but these same factors permitted controlled experimental operation with a small compressor installation and with a large number of monitor wells. These were needed for adequate observation of the underground phenomena at reasonable cost. RESERVOIR CHARACTERISTICS The reservoir chosen for the experimental field tests was a 124 thick section of tar sand extending from 49 to 61 ft subsurface, with shale and siltstone laminations sealing the top and bottom. This section was part of a larger 30-ft thick tar sand deposit which extended both above and below the test zone. Core analyses showed that the 12-ft sand was effectively subdivided into two approximately equal sections, with the lower zone being consistently more permeable than the upper zone. The most significant laboratory core data are summarized in Table 1. The line drive test which is the principal subject of this report utilized only the lower 6-ft thick zone, with the upper zone regarded as part of the 55-ft overburden. WELL PATTERNS The over-all field test program involved a total of seven different well patterns, including conventional five-spots and seven-spots plus a 15-well line drive pattern and a 10-well radial pattern. In some of the tests the full 12-ft zone was employed; in other cases only the more perme-

Jan 1, 1967

By P. Halbach

Hydrothermal activity is well known from many locations on most mid-ocean ridges, but no hydrothermally mineralized area had yet been found at the ultraslow spreading southwest Indian Ridge up to October 98 when the Japanese RV Yokosuka with the submersible Shinkai 6500 investigated this area. A massive sulfide field was discovered near 27°51S / 63°56E in the 11th segment west of the Rodriguez Triple Junction. The Free University of Berlin had joined this cruise and taken over the responsibility for the study of the respective sulfide mineralizations. Hydrothermal minerals were sampled during two dives at a water depth of 2940 m close to the summit of an axial volcanic ridge called Mount Jourdanne. Massive sulfides occur on the seafloor as small smooth mounds with an average area of about 5 m2. Their surfaces are weathered and have a reddish to brownish colour. In addition to these mound-like structures, small tube-like chimneys were observed; these chimneys rise approximately 30 to 40 cm above the floor and are less than 10 cm in diameter. No indications of hydrothermal fauna could be detected. All the hydrothermal features are spatially related to faults and smaller fissures controlled by an E-W trending graben system crossing the summit region of the submarine volcano. Such tectonized areas are generally considered to be ideal for hydrothermal activity because they may have both a magmatic heat source in the deeper underground as well as pathways for the fluid circulation.

Jan 1, 2002

By John J. Henn

Ten proposed processes for the recovery of manganese from domestic resources as a high-grade oxide product are described. Nine of the processes employ sulfur dioxide, sulfuric acid, or a combination of both for leaching. The tenth process utilizes sulfur dioxide to sulfatize the ore at 600° to 850°C before water leaching. In addiction to these ten complete processes, six processes from the patent literature are described. Methods for receovering MnSO4?H2O are also reviewed.

Jan 1, 1968

By Richard L. Stein

INTRODUCTION Increasing a miner&apos;s chance of surviving a disaster requires advance planning for emergencies, adequate training of personnel, and the provision of proper survival equipment. It is extremely important that fires and toxic gases be detected early, and that warning systems such as stench, audible and visual alarms, and communications systems be provided to allow timely escape. However, situations do occur where timely warning is not provided and immediate escape is not possible, regardless of the precautions that are taken. Under such circumstances, a combination of new per¬sonal protective devices and old techniques can provide protection that is adequate to save a miner&apos;s life. SELF-RESCUE EQUIPMENT Self-rescuers are devices which provide a short-term supply of respirable air under the potentially lethal con¬ditions following a mine disaster. Functioning either as filtration devices for the elimination of carbon monoxide (CO) or as oxygen supplies, self-rescuers allow an endangered miner a limited amount of time in which to effect an escape or reach a place of temporary safety. Carbon-Monoxide Self-Rescuers For almost 50 years, filtration self-rescuers have protected miners&apos; lives following explosions or fires. Designed to eliminate carbon monoxide from inhaled air, the first of these devices was approved in the 1920s and has evolved into the two units that are approved today-the Mine Safety Appliance (MSA) W-65 and the Draeger 810. Both of these units rely on the cata¬lytic conversion of very toxic carbon monoxide to rela¬tively safe levels of carbon dioxide (CO,). As shown in Figs. 1 and 2, both of these filtration self-rescuers operate in the same manner. On inhalation, the mine air passes through both coarse and fine filters that remove the dust, preventing the dust from coating the chemical beds or entering the miner&apos;s mouth. The air then passes over a drying agent that removes water vapor; this is required to prevent the water vapor from poisoning the catalyst. Subsequently, the dried air passes over the Hopcalite catalyst, where carbon monoxide is converted to carbon dioxide. Then, the air passes through a heat exchanger that reduces the temperature of the inhaled air. Finally, the air is inhaled by the user. Air exhaled by the user passes through the heat ex¬changer and exits the device through an expiratory valve. Both units of this type are subject to certain limita¬tions: 1) The units do not protect the user against oxygen¬deficient air; when air is inhaled through this type of self-rescuer, the device only removes the carbon mon¬oxide. If the mine air contains less than 15% oxygen, anoxia is inevitable. Symptoms of anoxia include dizzi¬ness, shortness of breath, quickened pulse, and deeper and more rapid respiration while the victim is at rest. During heavy exertion such as would be expected dur¬ ing escape efforts, a 15% oxygen level can cause loss of consciousness. 2) The units do not protect against excessive levels of carbon dioxide. Available data on carbon monoxide and carbon dioxide concentrations following explosions or fires are limited, but there are indications that the carbon monoxide concentration can rise to 2% and the carbon dioxide concentration can reach 5 or 6% of the mine air (by volume). In some situations, the in¬haled air could contain up to 6 or 7% carbon dioxide. At a carbon dioxide concentration higher than 2%, breathing patterns can be affected adversely. At a con¬centration of 6 or 7%, the effects include severe respira¬tory distress, with unconsciousness resulting from exer¬tion such as that needed for escape activities. 3) The units do not protect against high inhalation temperatures. The catalytic oxidation of carbon mon¬oxide to carbon dioxide is an exothermic reaction that evolves a large amount of heat. As the carbon monoxide concentration increases, the temperature of the inhaled air also increases. Available data show that above 1.5% carbon monoxide, the air inhaled through some self¬rescuers can be as high as 90°C (194°F). At those

Jan 1, 1982

By A. English, M. J. Greaves

This paper is a discussion of pelletizing systems developed over the last 15 to 20 years for the agglomeration of fine iron ore concentrates. Five different pelletizing systems are now in commercial use in the U.S., and for the purposes of comparison, estimated operating costs and capital costs for the construction of four of them are included. Capacities of existing commercial plants are examined, together with the anticipated capabilities of plants presently being built or projected. In just 21 years, the art of pelletizing iron ore concentrates has reached maturity with mastery of the separation of finely divided concentrates from low-grade iron ores and their agglomeration into pellets containing about 65% iron. This accomplishment has firmly established an improved feed for the blast furnace, with resulting benefits in faster reduction of burdens and greater economy of operation. The present production capacity of pelletizing facilities in the U.S. is about 20 million tons annually, and it is expected to double by 1970. The rapid expansion of pelletizing in the U. S. has been closely observed in European countries, notably in Sweden and Germany, where pioneer agglomerating techniques were developed early in this century. PELLETIZING PLANTS AND PROCESSES Twelve commercial pelletizing plants are presently in operation in the U. S. and Canada. An equal number are in various stages of engineering and construction, and many others are being considered. The pelletizing systems currently employed include shaft furnaces, horizontal grates using three different airflow arrangements, and grate kilns. The capacity of pelletizing operations in North America is shown in Table I. All of these plants are integrated with the mine, the ore-crushing facilities and the concentrating plant and are equipped with storage and loading-out facilities for the product. Normally, a pelletizing plant is composed of a shuttle conveyor above the receiving bins; balling equipment; a heat-hardening system including the necessary auxiliaries such as furnaces, burners and controls, ducts, fans, meters and instrumentation; fines recovery equipment; and product handling equipment. Also included are the necessary auxiliaries and utilities such as boilers or power plant; oil unloading and storage facilities; coal unloading storage, grinding and distribution facilities; and bentonite or other additive storage and distribution equipment. Shaft Furnaces: Vertical shaft furnaces used in this country are limited to the treatment of natural magnetite concentrates containing minor quantities of residual fluxing elements. Fig. 1 shows a perspective view of the shaft furnace with balling, feeding and pellet-handling equipment. An elevation of a shaft furnace is shown in Fig. 2. A commercial shaft furnace unit is about 45 ft in height with a 6 x 14-ft rectangular cross section and has a nominal production rate of approximately 50 gross tons of pellets per hour. The upper portion of the furnace shaft is constructed of fire brick as protection from the high process temperatures involved. The lower portion of the shaft is lined with abrasion-resistant brick to withstand erosion from the fired pellets. Rectangular-shaped, refractory-lined and insulated combustion chambers are situated on each side of the shaft furnace. Oil or gas is burned to produce high temperature gases which are forced into the furnace through ports located near the top of the combustion chambers. The shaft furnaces operate at a pressure of approximately 6 psi. Pellets are fed into the top of the furnace by a pantographic feeder designed to produce the desired pellet stockline. The furnace is kept filled at all times and pellets are fed and discharged from the furnace at the same rate. In early development, 10 to 12 lb of solid fuel was incorporated in the pellets. However, the main source of process heat is now derived from the combustion chamber gases. In some instances no solid fuel is used. The pellet movement in the shaft furnace is counter-current to the flow of gases. Ambient air is introduced through louvers at the lower end of the furnace, at about 6 psi, cooling the fired pellets and supplementing the heat of the high temperature gases from the combustion chamber ports. The zone of maximum temperature, located above the ports of the combus-

Jan 1, 1963

By V. Koump, T. F. Perzak, R. H. Tien

A series of experiments were carried out in which the rates of propagation of the liquidus and the eutectic fronts Mere measured during essentially one-dimensional freezing of Al-Cu alloys. The dimensions of the ingots were 3 by 5 by 6 in. Three different alloys containing 0.1, 4.5, and 17 pct Cu were used in these experitments. For each alloy the rate of heat removal was varied to give a total jreezing time in the range 3 to 30 min. The results of these measurements cowlpared favorably with the theoretical model of freezing of binary alloys with time-dependent surface temperature. IN engineering analysis of solidification of commercia1 steels and nonferrous alloys it is a common practice to assume that an alloy freezes by propagation of an isothermal solidification front, i.e., essentially as a pure metal. In two recent theoretical investigations&apos;j2 the present authors explored the possibility of a more realistic approach to the problem of solidification of alloys. In the proposed model the freezing of an alloy is assumed to take place by propagation of two isothermal fronts, i.e., the liquidus front and the solidus (or eutectic) front. The region between the two fronts contains both liquid and solid and is referred to as the solid-liquid region. The width and the solid content of the solid-liquid region vary with alloy type, solute concentration, and cooling rate. For a given alloy system, initial concentration of solute, and the mode of heat removal, the proposed model yields the temperature distribution within the solid skin, temperature, solid fraction, and concentration distributions with the solid-liquid region, and the rates of propagation of the liquidus and the solidus fronts. This model is obviously of considerable practical importance in engineering analysis of solidification processes, since it gives a more realistic estimate of skin strength during solidification and a better estimate of the total freezing time. Before the new model can be used with confidence, however, it is necessary to test this model experimentally. The experimental testing of the proposed model is a relatively simple matter since the effects to be measured are large and a relatively simple experiment will suffice. The theoretical model predicts, for example, that during freezing of an alloy containing substitutional type solute (negligible diffusion in the solid during freezing) the solid-liquid region occupies an appreciable portion of the ingot, even at low concentration of solute.&apos; Another prediction of the theo- V. KOUMP, formerly with U. S. Steel Corp., is now with Research and Development Center, Systems and Process Division, Westinghouse Electric Corp., Pittsburgh, Pa. R. H. TlEN is Senior Scientist, Fundamental Research Laboratory, U. S. Steel Corp., Research Center, Monroe ville, Pa. T. F. PERZAK, formerly with U.S. Steel Corp., is now with Fiber Industries, Greenville, S. C. Manuscript submitted March 6, 1968. IMD retical model, easily verifiable by experiment, is that the rate of propagation of the solidus (or eutectic) front increases as the solidus front approaches the center of the slab. This prediction is contrary to well-known behavior of the solidification front during freezing of pure metals, where the rate of propagation of the solidification front decreases with time and freezing is completed at the lowest rate. A rather severe test of the proposed model is provided by comparison of theoretical predictions and experimental measurements of the effects of cooling rate and composition on the rates of propagation of the liquidus and the eutectic fronts. In order to test the soundness of the formulation and the method of solution of the problem of solidification of alloys a series of experiments were carried out in which the rates of propagation of the liquidus and the eutectic fronts were measured during essentially one-dimensional solidification of A1-Cu alloys. The A1-Cu system was chosen strictly as a matter of convenience. Three different alloys containing 0.1, 4.5, and 17 pct Cu were used in these experiments. For each alloy the rate of heat removal was varied to give the total freezing time in the range 3 to 30 min. The results of these measurements are compared with the predictions of the theoretical model of solidification of binary alloys, with time-dependent surface temperature.&apos; Before the experiments described in this paper were undertaken, a serious attempt was made to utilize the measurements of previous investigators to test the theoretical model. In the course of this preliminary study a careful review was made of experiments of Pellini and coworkers3 and Doherty and Melf~rd.~ The measurements in Pellini&apos;s work were carried out using a steel containing at least four major components. Evaluation of the solid fraction-temperature relation for this steel (required in the theoretical model) is difficult and uncertain. Doherty and Melford, on the other hand, measured the solid fraction-temperature relation experimentally, but did not give sufficient data to explore the effects of composition and the cooling rates on solidification. Hence it was not possible to utilize these measurements to test our theoretical model. EXPERIMENTAL METHOD The experimental technique used in this investigation differs somewhat from the more conventional techniques employed in solidification studies. This technique was developed primarily to eliminate con-vective mixing in the molten metal caused by pouring of molten metal into the mold. In our experiments A1-Cu alloys were melted directly in the mold. The mold assembly used in solidification experiments is shown in Fig. 1. The mold was fabricated from *-in. stainless-steel sheet. The dimensions of

Jan 1, 1969

By Donald Leroux, Simon Gariépy, Luc Lachance

"Quantitative information about the quality of metal balance results is often overlooked when making important plant production planning decisions. Not only is this common omission made in a context where many measurements taken in and around mineral processing plants carry significant errors, but it also conflicts with the AMIRA P754 Code of Practice for Metal Accounting. The fact that metal balances are typically published without any indication of data quality may give the wrong impression that the measurements are unquestionably accurate. While it is true that statistical data reconciliation can improve the confidence intervals of redundant variables, there is no data processing technique that brings them down to zero at a finite cost. In this paper, we review the entire data flow, starting from field instruments to metal accounting-based decision-making to show how measurement errors are transmuted into business risks associated with production planning. Necessary conditions for first exposing then quantifying such business risks are stated. Pitfalls to be avoided are also discussed. Finally, a simplified risk assessment and management procedure which considers the quality of metal balance results are applied to a polymetallic mineral processing plant. INTRODUCTION Each and every mineral processing plant has production reporting obligations. In this paper, we are concerned with metal accounting reports (Morrison, 2008) where saleable metal flows and inventories are estimated and published. These metal accounting reports are delivered to a variety of stakeholders who use them for internal management purposes (day-to-day plant production planning, plant operation optimisation, capital spending, etc.) as well as for external management (royalty settlements, tolling agreements, etc.). Hence, there should be no doubt that spotless metal accounting is instrumental to high-quality corporate governance (Gaylard et al., 2014) of mining and metallurgical companies. To this extent, one would have expected industry-endorsed standards to have emerged a long time ago. However, the lack of an accepted set of standard procedures for metallurgical accounting was explicitly recognized as an industry-wide problem only in August 2001 during an SAIMM workshop held in Cape Town, South Africa. Discussions that followed this workshop led to the initiation of the AMIRA Project P754, “Metal Accounting and Reconciliation”, in 2003."

Jan 1, 2015

By S. Sumski, M. B. Panish, R. T. Lynch

The liquidus isotherms in the gallium-rich corner of the Ga-Al-P phase diagram have been determined from 1000" to 1200°C and at I100°C the corresponding solidus isotherm was obtained. A simple thermody-namic treatment which permits calculation of the solidus and liquidus isotherms is discussed. A technique which was previously used for the growth of GaxAl1-xAs was used for the preparation of solution epitaxial layers of GaxAl1-xP and ALP. An approximate value of 2.49 i 0.05 ev for the band gap of Alp at 300°K was obtained and the ternary phase data were used to estimate a value of 36 kcal per mole for the heat of formation 0f Alp at that temperature. The Gap-A1P crystalline solid solution is one in which there exists the possibility of obtaining crystals with selected energy gaps, within the limits imposed by the energy gaps of Gap and Alp. Such crystals are of considerable interest because of their potential value for optoelectronic and other solid-state devices. Furthermore, it has been amply demonstrated for GaAs and GaP,&apos;-7 that device, or bulk materials grown from gallium solution generally have more efficient radiative recombination than materials prepared in other ways. This presumably due to the lower gallium vacancy concentration in such material.= Small crystals of GaXAl1-xP and A1P have been grown from solution,8-10 and A1P has been grown from the vapor," but neither have previously been grown by liquid epitaxy. In this paper we present the ternary liquidus-solidus phase diagram of the Ga-A1-P system in the region of primary interest for solution epitaxy, and discuss the thermodynamic implications of that phase diagram with particular reference to the liquidus and solidus isotherms in the gallium-rich corner of the GaxAl1-xP primary phase field and to the A1-P system. Several measurements of the absorption edge of GaxAl1-xP crystals have been made and the width of the forbidden gap of A1P has been estimated from these measurements. EXPERIMENTAL The differential thermal analysis technique used to determine the liquidus isotherms and the optical measurements used in this work are similar to those described previously12 for the Ga-Al-As system, ex- thermocouples in the thermopile for added sensitivity. The materials used were semiconductor grade Ga, Gap, and Al+ The composition and temperature range at which DTA studies could be done was quite restricted. The upper temperature was limited by the chrome l-alumel thermopile to about 1200°C, and the highest aluminum concentration to about 5 at. pct by low sensitivity caused by the reduced solubility of Gap with increasing aluminum concentration in the liquid. DTA studies were not possible at 1000°C and below because of the low sensitivity caused by low solubility of Gap in the Ga-A1-P system. The cooling rate for these studies was about 1°C per min. No heating studies were done because of limited sensitivity. Supercooling probably does occur, but our experience with other 111-V systems indicates that it is no greater than about 10 to 15.c. Solid solubilities were determined by analyzing epitaxial layers of GaxAl1-xP grown from the liquid, with an electron beam microprobe. The layers were grown on Gap seeds by a tipping technique in which the layer is grown over a short-temperature range (20" to 50°C) on the seed from a solution of known composition. The tipping technique reported by Nelsson1 for GaAs could not be used, particularly for solutions containing appreciable amounts of aluminum, because of the formation of an A1203 scum on the liquid surface. A system was therefore designed, which would effectively remove the oxides mechanically, so that uniform wetting and crystal growth could occur. This tipping technique has already been described in detail." The best control over the composition of the re-grown layer was obtained when the tipping was done at a temperature which corresponded to the temperature of first formation of solid for the solution being used. Generally, therefore, a solution was prepared by adding the amounts of Ga, Gap, and A1 required to yield a solution which would be completely liquid above the tipping temperature with solid precipitating below that temperature. For most of the work reported here, the 1100°C isotherm of the ternary was used. It was generally necessary to heat the solution to 50" to l00. C above the tipping temperature to dissolve all of the Gap in a reasonable length of time. The epitaxially grown layers were used both for optical transmission measurements to aid in the estimation of the way in which the absorption edge changed with aluminum concentration, and for the electron beam microprobe analyses to provide data for the determination of the solid solubility isotherm. RESULTS AND DISCUSSION Liquidus Isotherms in the Ga-A1-P Ternary Phase Diagram: Thermodynamic properties of the system. The only thermal effect studied in this work was that

Jan 1, 1970

By J. E. Dutrizac, R. J. C. MacDonald, T. R. lngraham

When sintered disks of synthetic chalcopyrite (CuFeS2) were leached in acidified aqueous solutions of ferric sulfate, the following reaction stoichiometry was obtained: CuFeS2 + 2Fe2(SO4)3 = CuSO4 + 5FeSO4 + 2S Over the temperature range from 50º to 94ºC, the reaction displayed parabolic kinetics. The parabolic rate constant for the dissolution of copper is given by the equation: log.k(mg2/cm4-hr)= 11.850 - 3780/T The activation energy for the dissolution process is 17 ± 3 kcal per mole. The parabolic kinetics have been attributed to the progressive thickening of a sulfur film on the surface of the chalcopyrite. When the leaching solutions contain less than 0.01 molar Fe+3 , the Fe concentration influences the rate of leaching, probably through a mechanism involving the diffusion of ferric sulfate through the sulfur layer. At higher Fe+3 concentrations, the rate control in the leaching. reaction has been attributed to the diffusion of ferrous sulfate through the sulfur. The rate of reaction is insensitive to changes in acid concentration and in disk rotation speed. ThE reaction of acidic ferric sulfate solutions with various sulfide minerals is of practical interest for both bacterial and heap leaching. This leaching medium is generally used with low-grade ores that cannot be treated profitably by conventional means. In both bacterial leaching1-3 and heap leaching, the active agent for sulfide dissolution is ferric sulfate. Although the reactions of ferric sulfate with chalcocite, covellite, and bornite have been investigated,4*7 the kinetics of leaching chalcopyrite with ferric sulfate have not been thoroughly studied. This paper reports a study of that reaction. EXPERIMENTAL Reagent-grade sulfur was purified by the method of Bacon and FanelliB and then it was vacuum-distilled to remove any soluble magnesium salts that had been introduced during the purification procedure.9 From stoichiometric quantities of the purified sulfur and hydrogen-reduced electrolytic copper sheet (99.90 pct Cu), CuS was synthesized at 450°C in a vacuum-sealed, pyrex vessel. About 24 hr was required for the completion of the reaction. A similar procedure involving hydrogen-reduced iron wire (99.90 pct Fe) was used to synthesize FeS1.002. A 2-furnace arrangement was required. The iron was heated to 800°C while the sulfur was maintained at about 400°C. Although the reaction to consume the sulfur was rapid, the material required additional heating (1 week) in a sealed silica ampoule at 800°C before it was homogenized. X-ray powder diffraction analysis confirmed that the copper sulfide was covellite and that the iron sulfide was troilite. The composition of the iron mineral was confirmed by wet chemical analysis. The two sulfides were ground to minus 100 mesh, weighed in equimolar amounts, mixed thoroughly, and pressed into pellets at 80,000 psi. The pellets were vacuum-sealed in pyrex ampoules and then sintered for 3 days at 550°C after an initial heating at 450°C for a few hours. The pellets were then cooled, polished with 3/0 emery paper, rinsed in acetone, and stored. The material had the characteristic brassy color of chalcopyrite and was shown by X-ray diffraction to be CuFeS2. Microscopic examination of the polished surfaces revealed small inclusions of pyrite (approximately 0.5 vol pct) as the only impurity. The presence of small amounts of a second iron compound will not alter the amount of dissolved copper but might increase the amount of ferrous ion slightly. It was calculated that dissolution of all of the pyrite and 100 mg of Cu (a typical value) would change the expected ferrous concentration by only 4 pct. Microscopic examination of a pellet after leaching revealed that the pyrite was not preferentially solubilized; only those pyrite grains at the surface were attacked. Hence, the pyrite is unlikely to alter the rate of copper dissolution. The chalcopyrite disks were about 1.7 mm thick and 27 mm in diam. They were about 80 pct of theoretical density, and for this reason their true reaction area was somewhat larger than the 5.8 sq cm area presented by the polished face. The disks were cemented to lucite cylinders in such a way that only the polished face was exposed. The disks were then leached by methods previously described.6,7 RESULTS AND DISCUSSION Stoichiometry and Kinetics. The initial experiments were directed to the problem of resolving the stoichiometry of the leaching reaction. Disks of CuFeS2 were leached at 80°C for various periods of time in acidified ferric sulfate solutions that were protected from oxidation by a cover of flowing nitrogen. When the disks had been partly leached, they were removed, their soluble salts were washed out, and then they were treated with CS2 in a Soxhlet extraction apparatus. The ratio of elemental sulfur to dissolved copper thus obtained was approximately 2 to 1. After the extraction of elemental sulfur from the pellet, the residue consisted of unreacted chalcopyrite only. For runs in which an appreciable amount of copper was dissolved, the ratio of ferrous ion to cupric ion in the solution was

Jan 1, 1970

By L. L. McDaniel

Copper smelters of various kinds have operated in the Morenci district since 1872, but all have been abandoned with the exception of the present Morenci Smelter of Phelps Dodge Corporation, which was completed in 1942. During the five-year period starting in 1937, the Morenci ore body was prepared for open pit mining, pilot mill test work was carried out, and a complete reduction works, of which the Smelter is a part, was designed and erected. Actual construction work on the Morenci Smelter was started in the fall of 1940, and warming up of the units began on April 1, 1942. Charging of the reverberatory furnaces commenced on April 18, 1942, and the first anode copper was produced on April 26, 1942. The smelter was originally designed to handle the production of the Morenci Concentrator on a 25,000 ton per day program, but by the time the smelter was in operation, plans were already underway to increase the smelter capacity to handle the production of the concentrator which was being enlarged to 45,000 tons a day capacity as a war-time necessity. This extension to the smelter was completed and the new units were put in operation toward the beginning of 1944. The original smelter consisted of a smelter crushing plant, bedding plant, two direct-smelting reverberatory furnaces with two waste-heat boilers on each furnace, three converters, an anode department, a stack, and all of the usual accessory smelting equipment. The extension consisted of increasing the bedding plant from three to five beds, the reverberatory department from two to four furnaces, and from four to eight waste-heat boilers, and the converter department from three to six converters. A third converter aisle crane was added and additions were made to the flue systems and conveyor systems throughout the smelter; but no change was made in the smelter crushing plant or the anode department, and the same stack was used for all additional Smelter units. A blister casting machine was installed at that time in the south end of the converter aisle to handle excess and emergency production above the capacity of the anode department and in 1947 a converter aisle skull breaker and a lime burning plant were added as the final units for a complete plant. The choice of direct smelting over calcine smelting for the Morenci Smelter was made after careful study by members of the Western organization of Phelps Dodge Corporation and after test runs on direct smelting of Morenci concentrate had been made at the Douglas Smelter of Phelps Dodge Corporation. The Morenci furnace charge is made up of comparatively high grade concentrate with no ores of smelting grade available and with only flux, a small amount of copper precipitate and the usual amount of smelter secondaries to be smelted with the concentrate. The simplicity of direct smelting for this charge and the large amount of waste-heat steam available from direct smelting operations were factors influencing the decision to adopt direct smelting for Morenci. The design of the Morenci Smelter and the type of units selected followed best experience at the Douglas Smelter of Phelps Dodge Corporation. A description of the original smelter before operations started was given in an article in the May 1942 issue of Mining and Metallurgy. The purpose of the present article is to describe the enlarged Morenci Smelter, with a discussion of metallurgy and operating practice and to show tabulations of operating and metallurgical results obtained. Because of beginning operations during the early years of World War 11, many problems caused by labor shortage were encountered, but no major difficulties developed in starting the new plant. However, because of labor shortage, full scale Smelter production was not reached until the fall of 1946. Fig 1 shows a general plan of the Morenci Reduction Works. The arrangement of the smelter equipment is shown in Fig 2, a sectional view of the smelter is shown in Fig 3, and the smelter flow sheet is shown in Fig 4. Metallurgy The metallurgy of direct smelting, being more or less fixed by the character of the charge, is not subject to the control available in calcine smelting. Slags may be modified by the addition of suitable fluxes, but the grade of the matte is determined almost entirely by the iron:copper ratio of the concentrate. The direct smelting operation involves distributing the wet concentrate along the sidewalls and in the bath of a reverberatory furnace by means of some suitable feeding device and raising the temperature of the charge so that first the moisture is driven off, then the first-atom sulphur is eliminated, and finally the sulphide portion of the charge melts and runs into the bath, carrying with it the non-sulphide portion which has been partially fluxed to form a suitable slag. The fusion of the non-sulphide portion is completed by contact with the irony converter slag which is regularly being poured into the reverberatory furnace. The smelting rate of the charge is influenced by the mineralogi-cal composition of the sulphide portion of the concentrate and by the composition and amount of the non-sulphide portion including the fluxes added. The copper in Morenci concentrate is chiefly in the form of chalcocite, intimately associated with pyrite, and non-sulphide content is very low so that

Jan 1, 1950

By Harry C. Gatos, Frank J. Bachner

It was shown through high-pressure experiments that tin loss by volatilizatim is necessary for the degrada-tion of the superconducting transition temperature of Nb,Sn associated with high-temperature annealing. Crystallochemical analysis of the degraded Nb3Sn showed that it constitutes a new phase with ordered niobium-site vacancies, created by the migration of niobium atoms to vaccnt tin sites. This new phase was found to form when 4 pct Nb-site vacancies were present. It has a transition temperature of 6&apos;K and a lattice parameter of 5.283A. A similar degradation effect was observed in Nb,Al. Its superconducting transition temperature dropped from 16.5" to 8" K following a high-temperature annealing. The superconducting temperature degradation in these 0-tungsten structure compounds is attributed to the disruption of the interchain d bonding by the periodic interruption of the niobium atom chains. By annealing the degraded Nb, Sn at 1000 C in nitrogen its normal superconducting behavior is restored most likely due to the incorporation of nitrogen atoms causing the elimination of the ordered vacancies. HANAK et al.&apos; have observed low superconducting transition-temperature values (T, - 9"K) in some NbsSn samples deposited from the vapor phase. They attributed such low T, values to disorder in the 0-tung-sten structure. Much lower T values (down to 5.6"K) were reported by Reed et al.zC for NbsSn samples annealed at high temperatures. These authors also attributed this degradation effect to disorder (random occupation of the A and B sites by niobium and tin) but pointed out that such disorder could be brought about (by high-temperature treatment) only in samples containing niobium in excess of the stoichiometric composition NbsSn. Both groups reported that the normal superconductivity behavior could be rever-sibly restored by appropriate heat treatment. Courtney et al., also found that degradation in NbsSn requires excess niobium brought about by the loss of tin during the treatment. However, these investigators proposed that the degradation is due to niobium-site vacancies resulting from the migration of the niobium atoms to the vacated tin atom sites. They did not consider the reversibility of the effect. The present study attempts to establish the nature of the above degradation phenomenon. EXPERIMENTAL PROCEDURES All compounds prepared for this investigation were made from the powders or filings of the elements which were intimately mixed, cold-pressed into a cylindrical pellet at approximately 50,000 lb per sq in., and then submitted to the desired heat treatment. The samples annealed under high pressure were placed in a MgO sample container which was mounted in a pyrophyllite tetrahedron designed for a tetra-hedral-anvil press. Details of the experimental arrangement are given elsewhere. This setup allowed heating at 1800°C or above under pressures in excess of 30kbars for 3 hr. The samples annealed in a vacuum were prepared in a high-temperature vacuum furnace which could reach temperatures up to 2400°C under a pressure of 2 x lo-&apos; Torr. For annealing in a reactive atmosphere, a quartz tube was placed in a clamshell furnace and the desired gas ambient passed through the tube. Lattice parameters were determined using a Debye-Scherer 114.6-mm camera. Cohen&apos;s method, programmed for the IBM 7094 computer, was used to calculate the lattice parameter from the measured d spacings. X-ray integrated intensity measurements were made on several samples. These samples were ground to -400 mesh and the powder mixed with a solution of collodion in amyl acetate. The mixture was poured into a depression milled in a bakelite disc. When the mixture dried, the surface of the disc was ground flat leaving a diffraction surface defined by the face of the disc. The disc was mounted in a Philips rotating specimen holder which allowed the rotation of the sample in the plane of the diffraction surface and the integrated intensity measured using a scintillation counter and a pulse-height analysis sys-tem. The superconducting transition temperatures were determined by means of self-inductance techniques.&apos; EXPERIMENTAL RESULTS AND DISCUSSION The Role of Tin Loss in the Degradation of Super-conductivity. The loss of tin during high-temperature annealing can be effectively suppressed by annealing under high hydrostatic pressures. Accordingly, a series of experiments were performed under pressures of approximately 30kbars. This pressure was the minimum under which high-temperature experiments could be safely performed in the particular pressure apparatus employed. Experiments were also designed to test high-pressure effects on the superconductivity behavior of NbJSn. The results of the high-pressure annealing experi-ments are summarized in Table I. All samples were prepared as described earlier. They were reacted and homogenized at 1000°C for 24 hr under argon at-

Jan 1, 1967

By H. K. Birnbaum

The effect of 1ow-temperature stabilization anneals on the structure of the 0 phase Au-Cd alloys and on the diffusionless transformations observed in these alloys was examined by X-yay diffraction techniques. A phase separation in the ß-phase region was proposed to account for the experimenta1 results. The effects of quenching from elevated temperatures on the transformation behavior of these alloys were shown to be consistent with the proposed mechanism. IT has been shown that the high-temperature ß phase (CsCl structure) of the Au-Cd alloy system transforms to a phase having an orthorhombic (D2) ß&apos; structurel1-3 for compositions near 47.5 at. pct Cd and a tetragonal (4/m, m, m) ß" structure* in the vicinity of 50.0 at. pct Cd. Both transformations are diffusionless, crystallographically reversible, and occur on cooling at about 60° and 30°C respectively. The temperature interval from the beginning to the end of the transformation is of the order of 5°C in each case. Although the transformations are normally athermal, some of them have been reported to occur isothermally.= wechsler6,7 has shown that the effects of quenching a 49.0 at. pct Cd alloy from elevated temperatures are consistent with the retention of a nonequilibrium number of lattice vacancies. Annealing of these quench effects results in a broadening of the X-ray reflections.8 After a suitable quench, the 47.5 at. pct Cd alloy transforms to a phase having not the p&apos; orthorhombic structure but another structure which has properties similar to that of the ß" tetragonal structure.5.9 This change in the type of transformation has also been obtained after long anneals in the ß-phase region at about 70oC10 The present investigation was primarily concerned with the structural changes accompanying the above transformation phenomena. The change in transformation product and accompanying physical changes during an anneal in the ß phase have been termed stabilization effects. Experimental Procedure —The results reported in this investigation were obtained with the use of a Norelco diffractometer fitted with a temperature-controlled cryostat. The specimen temperature was controlled to better than ± 0.l°C during the measurements. CrKa radiation monochromated electronically with the use of a scintillation counter and pulse height analyzer was utilized. Specimens containing 47.5 and 50.0 at. pct Cd were prepared by sintering filings obtained from homogenized ingots of the proper alloy composition. (Gold of 99.999 pct purity and cadmium of 99.98 pct purity were used). All heat treatments were carried out with the specimens capsulated in vacuum ( < 10 % mm Hg) or in a He-H gas mixture. The quenching technique used in these experiments was to drop the pyrex capsule which contained the specimen from the annealing furnace into water, the temperature of which was controlled. The pyrex capsule shattered on contacting the water resulting in a relatively rapid quench. After the heat treatment, the specimens were mounted in the diffractometer and were left undisturbed in the diffractometer specimen holder during each sequence of measurements. EXPERIMENTAL RESULTS A) Low-Temperature Annealing—The transformations which were considered "normal" for these alloys were those obtained athermally during furnace cooling at approximately 50°C per hr after an elevated temperature anneal. Under these experimental conditions, the specimens were observed to transform to phases having structures whose diffraction patterns could be indexed as the ß&apos; orthorhombic structure for the 47.5 at. pct Cd and as the 0" tetragonal structure for the 50.0 at. pct Cd alloys. The transformation temperatures on cooling were approximately 60" and 30°C, respectively. Under the "normal" conditions both transformations were observed to go to completion, i.e., the entire volume of the ß phase was transformed to the product phase. In some specimens an extremely weak ß 110 reflection was observed at 20°C indicating that a small amount of retained ß was present. The effect of low-temperature annealing on the nature of the diffusionless transformations was examined for the 47.5 and 50.0 at, pct Cd alloy. The specimens were annealed in evacuated capsules at temperatures in the vicinity of 600°C (as specified in Table I) for 24 hr and were then cooled to 100°C at a rate of 50°C per hr. The specimens were then removed from the capsules and mounted in the diffractometer without allowing the specimen temperature to drop below 80°C. Annealing at the low temperatures was accomplished in the diffractometer by means of the cryostat which was mounted around the specimen. During the low-temperature anneals the lattice parameter, integral breadth of the reflections, and ratios of the integrated intensities of the fundamental and super lattice reflections for the 0 cubic phase were periodically determined. After annealing for the required time, the specimens were slowly cooled in the diffractometer and the diffraction patterns were recorded as a function of temperature. The specimens were cooled until the phase transformations were completed, following which the specimens were heated and diffraction

Jan 1, 1960

By T. E. Newkirk

In the past few years there has been considerable controversy on the most suitable material to be used in ventilation doors which will have to serve also as fire doors. For this reason it was thought useful at Mclntyre to find out to what extent our zinc chloride treated spruce doors were fire resistant and what protection we could expect in case of an underground fire. The doors to be tested were constructed of the same material as that used in our regular ventilation doors underground, namely, 2-inch tongue-and-groove well seasoned spuce. It is to be noted, however, that whereas the dimensions of the ventilation doors are 5 ft. by 6 ft., those of the test doors were only 14 in. by 17½ in. The treated doors were made up from lumber that l1ad been treated with chromated zinc chloride, as described in Mr. Keeley&apos;s paper. Two kinds of tests were carried out: a heat test and a flame test. An electric muffle furnace for assaying, equipped with a pyrometer, was used for the beat test, the furnace door being replaced by the wooden door to be tested. In the flame test, the door to be tested formed one end of a rectangular steel box in which was placed a large blow-torch. Air was admitted at the rear of the box. A pyrometer recorded the temperature at the inside surface of the door where flame impinged. The results of the tests are presented in the accompanying table, in which the word &apos;failed&apos; is to be interpreted as meaning that the door had been damaged to the extent that smoke, but not necessarily flame, issued from its outside surface.

Jan 1, 1949

By Francis M. Walters

THE problem of making iron-manganese alloys of scientific purity is a rather difficult one. They cannot be prepared in air because of the readiness with which the metals oxidize at the temperature of melting; and they cannot be prepared in vacuum because of the, high vapor pressure-of- manganese. The very property of: manganese which permits it to be purified interferes with the utilization of the best method of making pure alloys. Accordingly, it is necessary to use a gas atmosphere which will not affect the-properties of the alloys. The gases available for the purposes are hydrogen; helium and argon. Nitrogen forms intermetallic compounds with manganese very readily. Hydrogen, while valuable as a deoxidizer and having the advantage of being comparatively cheap, is explosive over a wide range and, has a rather high thermal conductivity. Helium is reported as, costing little but is difficult to secure at a reasonable price and also has a conductivity nearly as high as hydrogen. Since argon has a sufficiently low thermal conductivity, it has been selected for use in one induction furnace for melting, under a controlled, gas atmosphere, in spite of its cost, which is so high (70 cents to $1.50 per cubic foot) that it must be stored and purified.. Such a gas atmosphere-as argon makes necessary the use of the, high-frequency induction method of heating. This involves, a non-metallic container for the gas; .which is most conveniently of fused quartz or glass. The next

Jan 1, 1929

By Yunhua Gan, Xiaowen Chen, Meilong Hu, Haige Li, Yang Tong

Ethanol is a kind of renewable fuel, which can be produced from biomass and applied in many energy areas, such as motorcar. The combustion of ethanol in meso-scale is facing great challenges, such as great heat loss, poor stability, and low combustion efficiency. Electro-spraying technique is an effective method to atomize liquid ethanol due to its great advantage of monodisperse and uniform characteristics. In present study, electro-spraying was applied in liquid meso-scale combustor to produce very small droplet diameter and uniform droplet distribution. Experiments were carried out based on nozzle-ring-mesh electrode structure using pure liquid ethanol as fuel. Electro-spraying characteristics were measured by Phase Doppler Anemometer (PDA) under different nozzle voltages, ring electrode voltages, flow rates, and steel mesh positions. The results may be helpful to the design of new meso-scale electro-spraying combustor using renewable liquid fuel.

Mar 1, 2017

By K. L. Komarek, P. F. J. Landler

Synthetic polycrystals of wustite were reduced ilz H2-H2O mixtures over limited roncentration ranges wiltun the wustite. field and the weight changes were continuously followed with a McBain quartz spiral balance. The reduction was. found to be controlled by a combined surface plus solid-state diffusion reaction. The solid-state diffusion had an activation energy of 38 kcal. Self--diflusioities of iron decreased with itzcreasing vacancy concentration. The activation energy of. the surface reaction runs different tor- different samples. The surface reaction-rate constan increased with increasirzg vacancy concentration. THE reduction of the oxides of iron has been studied for many years. Edstroem&apos; has summarized the early work and has provided much information on the reduction of magnetite and hematite by hydrogen and carbon monoxide. More recent summaries are those by smeltzer2 and Themelis and Gauvin.3 Most investigators have reported that the iron metal which forms the outer layer during gaseous reduction is rather porous. According to Kohl and Engel14 the formation of such a porous iron layer depends on the properties of the underlying wiistite layer, on the reaction of the gas with the wustite surface, and on the transport of matter through the wustite layer. McKewan, Quets, Wadsworth, and Lewis, and Knacke 10 have found that, if a porous iron layer is formed, a surface reaction between gas and wustite at the bottom of the pores controls the rate of reaction. Seth and ROSS 11 and Warner 12 have pointed out that the influence of the gaseous pore diffusion through the porous iron layer cannot be neglected. It has further been shown that the wiistite layer formed during reduction is dense and that transport of matter across the layer occurs only by solid-state diffusion of iron ions.13,14 The solid-state diffusion rates observed by Edstroem and Bitsianis 14 and the surface reaction rates observed by Quets eta1.&apos; show that an interaction of the two steps in controlling the reaction rate has to be considered. In this investigation the reduction of wustite was studied with respect to the interaction of the two steps, isolated from any other effects, by reducing wustite within the wustite field from higher to lower oxygen concentrations with H2-H2O gas mixtures. A similar study with CO-CO2 mixtures has been performed by Levin and wagner.15 Fused synthetic wustite polycrystals were reduced in steps of 0.4 wt pct from 24.4 to 23.2 wt pct 0 and over a temperature range from 700" to 1050°C. A few tests were also conducted with reduction steps from 24.4 to 23.6 wt pct 0 and 24.5 to 23.2 wtpct0. The Fe-O phase diagram is shown in Fig. 1 where the composition of the gas phase in equilibrium with the condensed phases is plotted as pct H2 vs the temperature. A careful study of the literature led to the conclusion that the fully drawn equicomposition curves (in wt pct O) in the wustite field used by Edstroem 1,16 and other authors needed some correction. Based on results by Darken and Gurry17 (shown as open circles) and on some of our own data, four corrected curves for 23.2, 23.6, 24.0, and 24.4 wt pct O were calculated (drawn as dashed lines in Fig. 1) which should replace the fully drawn equicomposition curves. MATERIALS AND APPARATUS Materials and Specimen Preparation. Wustite was prepared from iron sulfate (Fisher Scientific Co., New York) which had a purity of over 99.92 pct, with small amounts of manganese, copper, and zinc adding up to 0.03 pct. From the aqueous solution iron oxalate was precipitated and decomposed to magnetite according to Economos. 18 The magnetite powder was pressed into cylinders and sintered in vacuum at 900°C for several hours. The sintered compacts were placed in a platinum crucible of 2.5 cm diam which was fitted into a high-purity alumina crucible and then inserted into the center of the graphite heating element of an electric resistance furnace.lg The furnace was evacuated to below 1 p Hg and the magnetite sample was slowly heated. The evolution of gases during heating deter-

Jan 1, 1967