Search Documents

By C. E. Lundin, M. Hansen, D. J. McPherson

PRIOR work on the Zr-Cu phase diagram by Alli-bone and Sykes,' Pogodin, Shumova, and KUGU cheva,' and Raub and EngeL3 as confined largely to copper-rich alloys. The investigations of Raub and Engel were the most recent and seemingly the most complete of these. Alloys from 0 to 68.3 pct Zr were studied principally by thermal analysis and microscopic examination. These authors reported an inter metallic compound ZrCu, (1116°C melting point) and two eutectics, one at 86.3 pct Cu (977°C mp) and the other at 49 pct Cu (877°C mp). The solubility of zirconium in copper was reported to be less than 0.1 pct at 940°C. The zirconium melting stock consisted of Westing-house "Grade 3" iodide crystal bar (nominally 99.8 pct pure). It was treated by sand blasting and pickling (HF-HNO, solution) to remove the surface film of corrosion product, resulting from grade designation tests. The crystal bar was cold rolled to strip, lightly pickled again, and cut into pieces approximately 1/32 in. thick and 1/4 in. square. These were cleaned in acetone, dried, and stored for charging. The high-purity copper (spectrographic grade) was supplied by the American Smelting and Refining Co. with a nominal purity of 99.99 pct. These copper rods were rolled to strip, cut into squares the same size as the zirconium platelets, cleaned in acetone, dried, and stored. Equipment and Procedures The equipment used for melting and annealing the zirconium binary alloys and for the determination of solidus curves has been described in connection with previous work on the Ti-Si system' and in recent papers in this series describing the studies on eight binary zirconium systems.5-' Techniques employed for preparing and processing the alloys were also similar to those used in the above references. Ingots of 20 g were melted under a protective atmosphere of helium on water-cooled copper blocks in a nonconsumable electrode (tungsten) arc furnace. The ingots were homogenized and cold-worked prior to isothermal annealing to aid in the attainment of equilibrium. The specimens were heat-treated in Vycor bulbs sealed in vacuo or under argon, depending on the temperature of the anneal. Quenching was accomplished by breaking the Vycor bulbs under cold water. Temperature control was within ±3OC of reported temperatures. Thermal analysis was primarily relied on to determine eutectic levels, peritectic levels, and compound melting points. The induction furnace incipient melting technique was also used but did not provide the accuracy obtained by thermal analysis in this system, which involves much lower solidus temperatures than the other zirconium systems. A special technique for the determination of characteristic temperatures was employed in the case of several intermediate phases and their eutectics which displayed very small differences in melting temperatures. Specimens were sealed in Vycor bulbs and annealed at a series of very accurately controlled temperatures. Metallographic examination was then employed to reveal incipient melting. Furnaces and techniques in general were described previously.' The echant used was 20 pct HF plus 20 pct HNO3 in glycerine unless otherwise stated. Results and Discussion The chemical analyses of the majority of alloys prepared for the determination of phase relationships in this system are given in Table I and a brief summary of the equilibrium anneals employed is given in Table 11. In a preliminary program, alloys containing 1, 4, and 7 pct Cu were annealed for three different times at each of the temperatures 700°, 800°, and 900°C. No change in the relative amounts of phases present was detected after 350, 150, and 75 hr at the above temperatures, respectively. The times listed in Table II were accordingly chosen as a result of these preliminary tests. Zirconium-rich alloys containing from 0.1 to 10 pct CU were reduced by cold pressing from 58 to 8 pct, depending upon thk alloy content, homogenized for 7 hr at 900°C, and then reduced 80 to 13 pct by cold rolling, again depending upon copper content. Other alloys were studied in the cast, or cast and annealed conditions. The contracted scope of investigation for this system included the range 0 to 50 atomic pct Cu. This approximate region is shown in Fig. 1. Due to evidence of phase relationships departing considerably from those proposed by Raub and Engel" in the 50 to 100 atomic pct range, the investigation was extended to cover this composition area rather thoroughly also. Fig. 2 is a drawing of the entire diagram. The labeling of some phase fields was omitted in Fig. 2 for the sake of clarity. An expanded view of the zirconium-rich region, with the experimental points necessary for its construction, is given in Fig. 3. The generally accepted value of Vogel and Tonn8 or the allotropic transformation a + 862' ±5OC, was employed in the construction of these diagrams. A careful study revealed that the "Grade 3" crystal bar used in this investigation actually transforms over the approximate range 850" to 870°C, due to impurities. It must be expected that this two-phase field in unalloyed zirconium will cause some departures from binary ideality in the very dilute alloys. Zirconium-rich Alloys: The a + ß transformation temperature is decreased from 862" to about 822°C by increasing amounts of copper. Thus, a eutectoid reaction, fi ß a+ Zr,Cu, occurs at a composition of about 1.6 pct Cu. The eutectoid level was determined to lie between the alloy series annealed at 815" and 830°C. The placement of this eutectoid temperature

Jan 1, 1954

Percolation infers the passage of a liquid through, the interstices of any material or materials permitting it. Leaching is the process of extracting soluble matter by percolation. Lixiviation is analogous to leaching. Percolation and leaching may occur simultaneously. A filter may be used either to strain suspended or finely divided matter from a liquid, when it is known as a clarifier, or to separate a liquid from a solid. Clarification usually infers the addition d: some settling or flocculating agent which permits the decantation of the clear supernatant liquor. The simple separation of solid from liquid, such as occurs when a thickened flotation concentrate is filtered, is usually termed dewatering. The word filtration is used more to cover the complex process of separating, as far as possible, solid from liquid by vacuum or pressure, removing the residual solution by wash, and at the same time leaching any recrystallized, absorbed, or undissolved matter, by percolation with the solvent. The final product of metallurgical treatment should be reported as a recovery when the yield is refined metal. When the metallurgical operations are incomplete and a concentrated but not refined-product is obtained, the metal content should be reported as an extraction.

Jan 1, 1919

By Will H. Coghill, P. H. Delano, G. D. Coe

DATA concerning the actual net energy required for pulverizing coal are lacking from the literature on coal pulverization. Power data given in the literature concern gross power and frequently include the power expended on the air blast or product-conveyor system, as well as power lost through friction in the pulverizer itself. Consequently, such data supply no information regarding the net energy consumed in pulverizing or the relative grinding resistance of various coals. In the study of coal pulverizing much work has been done on what is known as "grindability-index numbers," but grindability tests have seldom considered the energy input (that is, the "cause" part of the system "cause and effect"). There are many records of the effect, but even these have questionable value because the "grindability" tests did not make a pulverized product by a method comparable with commercial pulverizers. In many of the tests, only a selected part of the coal was ground, and the remainder continued to be an unknown factor. Furthermore, none of the grindability tests provide the balanced circulating load common to all modern commercial pulverizing. In order to obtain better understanding of the fundamental principles of coal pulverizing, the Bureau of Mines is investigating the "cause" phase; that is, the net energy input or net power excluding friction between the moving parts of the machine. As a first step in the investigation, it was necessary to design and construct a laboratory machine in which no friction-loss corrections are involved, which could grind and finish a minus-3/4 -inch feed, which could be emptied rapidly and completely, which could operate with a continuous feed and finish in an air separator; and, most essential of all, which would be equipped with a measuring device for recording only that portion of the total power consumed in actual pulverizing, hereafter referred to as "net energy input" or "net horse-powerhours." The channel-roller pulverizer here-inafter described is believed to meet these requirements. HISTORY OF THE MACHINE The work started when Ralph W. Smith, engineer, St. Genevieve Lime Co., St. Genevieve, Mo., was appointed one of the consultants of the Bureau of Mines, United States Department of the Interior, in cooperation with the University of Alabama, to develop a machine for testing the abrasiveness of coal. Smith had already developed a machine for testing the abrasiveness of dentifrices,1 and it was thought the same principles might be applied to coal. Smith's machine had a revolving disk with an annular channel in which the sample was placed. Riding in the channel was a small block or runner of selected soft metal held

Jan 1, 1942

By Gregoire Gutzeit

The development reported in this paper was begun by the author a number of years ago, while he was a lecturer on complex chemistry and metallurgy at the University of Geneva, Switzerland, and in charge of that institution's research laboratory. Completion of the development and reduction to practice did not occur until last year at the Westport mill, laboratories and testing plant of the Dorr Company, where this method is now in general use for identifying and localizing the mineral constituents of both metallic and nonmetallic ores. It has proved to be a practical tool of the metallurgical staff at the Westport mill, devising unusual milling flowsheets for complex and refractory ore bodies. In a number of instances the findings have been successfully used as fundamental factors in the design and specification of complete metallurgical plants. Seven examples of the use of this method in solving practical milling problems are included in this paper. General Outline The microscopic study of an ore, at first only of scientific interest, has proved extremely useful both in practical geology and in ore dressing. The binocular magnifying lenses for rough observation of the products of an ore-dressing plant have been in use for a long time; but only within the last few years has a systematic microscopical examination of ore samples become a normal tool of any research laboratory dealing with ore-dressing problems. Such an investigation avoids considerable loss of time as well as empirical trials and useless experimentation. It will generally indicate the correct grinding and often will suggest the proper method of treatment. . The petrographic determination of transparent minerals in thin sections, or even in grains, has been perfected, and very accurate methods have been devised to meet any requirement, such as Feodorof's rotating stage on the petrographic microscope. Almost all transparent minerals can be positively identified by their optical properties; i.e., isotropism, anisotropism, color, pleochroism, refractory index, cleavage, crystal form, birefringence, and others. The identification of opaque minerals is a much more difficult problem and can be done only by using polished specimens. Unfortunately, most of the valuable metallic ores, and even some of the nonmetallic ones, are not transparent; therefore it has been necessary to develop a special technique for the determination of these minerals. Some optical properties—for instance, isotropism, anisotropism, color, cleavage, reflecting power-—are often adequate in roughly classifying the mineral. Only "reflecting power" is a measurable value, provided special photometric equipment (ocular photometer or Orcel's photoelectric cell) is available. The other optical properties mentioned are more or less relative,

Jan 1, 1943

By Gregoire Gutzeit

The development reported in this paper was begun by the author a number of years ago, while he was a lecturer on complex chemistry and metallurgy at the University of Geneva, Switzerland, and in charge of that institution's research laboratory. Completion of the development and reduction to practice did not occur until last year at the Westport mill, laboratories and testing plant of the Dorr Company, where this method is now in general use for identifying and localizing the mineral constituents of both metallic and nonmetallic ores. It has proved to be a practical tool of the metallurgical staff at the Westport mill, devising unusual milling flowsheets for complex and refractory ore bodies. In a number of instances the findings have been successfully used as fundamental factors in the design and specification of complete metallurgical plants. Seven examples of the use of this method in solving practical milling problems are included in this paper. General Outline The microscopic study of an ore, at first only of scientific interest, has proved extremely useful both in practical geology and in ore dressing. The binocular magnifying lenses for rough observation of the products of an ore-dressing plant have been in use for a long time; but only within the last few years has a systematic microscopical examination of ore samples become a normal tool of any research laboratory dealing with ore-dressing problems. Such an investigation avoids considerable loss of time as well as empirical trials and useless experimentation. It will generally indicate the correct grinding and often will suggest the proper method of treatment. . The petrographic determination of transparent minerals in thin sections, or even in grains, has been perfected, and very accurate methods have been devised to meet any requirement, such as Feodorof's rotating stage on the petrographic microscope. Almost all transparent minerals can be positively identified by their optical properties; i.e., isotropism, anisotropism, color, pleochroism, refractory index, cleavage, crystal form, birefringence, and others. The identification of opaque minerals is a much more difficult problem and can be done only by using polished specimens. Unfortunately, most of the valuable metallic ores, and even some of the nonmetallic ones, are not transparent; therefore it has been necessary to develop a special technique for the determination of these minerals. Some optical properties—for instance, isotropism, anisotropism, color, cleavage, reflecting power-—are often adequate in roughly classifying the mineral. Only "reflecting power" is a measurable value, provided special photometric equipment (ocular photometer or Orcel's photoelectric cell) is available. The other optical properties mentioned are more or less relative,

Jan 1, 1943

Map

Jan 1, 1941

FRANCIS T. OMENS, ? Watsontown, Pa. (written discussion§).-In the second paragraph, Dr. Thwing mentions the various stages through which clay ware. must pass but he does not analyze the third stage, oxidation, suffficiently. There are two elements to dispose of in a great many, of the shales that must he burned; these elements are carbon and sulfur. Dr. Thwing speaks' of the carbon, but intimates that it is safe to have a temperature of -800° C., which we find to be rather dangerous on a great tiffany shales. With. one shale that we handle, we cannot go above 535° C. until we have passed this particular stage. At 800° C. the sulfur will begin-to pass off and it is very necessary that plenty of air be ad-

Jan 11, 1919

By J. C. Humbert, J. F. Elliott

The solubility of nitrogen in liquid pure Fe, Cr, and Ni, in liquid Fe-Ni, Fe-Cr, and Ni-Cr alloys and Fe-Cr-Ni alloys, has been measured by the Sieverts' type apparatus between 1500° and 1800°C. Tabulations and graphs of the solubility data and activity coefficients are shown. Heats of solution are reported. Interaction coefficients of the several elements in Fe. Cr, and Ni ave also reported. THE solubility of a gas in a liquid metal is usually measured by either the quenching technique or the so-called Sieverts' method. In the quenching method, 1-3 the melt is equilibrated at the desired temperature and pressure with the gas phase having a known fugacity of the gas being studied. The melt is sampled and the sample is quenched and analyzed chemically for its gas content. In Sieverts' method the melt is contained in a closed chamber. The apparent volume of this chamber, i.e. the "hot volume," is usually determined by introducing a known quantity of an inert gas having very closely the same physical characteristics as does the experimental gas. Alternatively, the experimental gas is used with an inert specimen having the same general physical characteristics as does the experimental melt. Subsequently, the experimental melt is equilibrated with the experimental gas by introducing a known quantity of the gas into the calibrated chamber. The solubility of the gas is obtained from P-V-T relationships. The quenching method suffers from' the limitation that some gas may be gained (as in the case of Cr-Fe alloys) or lost (as in the case of Fe-Ni alloys) during solidification and cooling of the sample. With Sieverts' method sampling and analysis are unnecessary. However, errors can result from the difficulty of determining accurately the "hot volume,"

Jan 1, 1961

By H. Van F. Furman

As the cyanide-method for the extraction of gold from ores is extensively used in the United States and elsewhere, and appears destined to prove a factor of increasing importance in the metallurgy of gold, a description of the latest laboratorymethods may prove of interest. The history of the development of the process in the United States has been analogous to that of all new processes. Many failures are to be recorded and a few successes. It is the opinion of the writer that, had the following simple tests been better understood, many of the failures would not have occurred, and we should probably have a larger number of successful plants in operation. While the process is not simple, but requires a high degree of chemical and engineering skill, the determination of the adaptability of an ore to the method is generally not difficult. While the laboratory-results will not always coincide with the actual results obtained in the mill, they will serve as a guide and control on the working of the mill, and mill generally suffice to determine if the ore can be

Jan 1, 1897

By L. D. Hall, S. J. Rothman

The diffusion of lead and of trace amounts of bismuth in liquid lead have been investigated by the capillary method, using ROD and ROE as tracers. The results are compared with existing theories of diffusion in liquids, the agreement with theory being fair. The heat of activation for self-diffusion in lead is found experimentally to be close to the corresponding activation energy obtained from viscosity data. The pioneer data of Groh and von Hevesi for the self-diffusion of liquid lead, using ThB as a tracer, fit in with the present results. OMPARED with the volume of effort expended on solid state diffusion, there has been little attention paid to diffusion in liquid metals. A review of experimental work in this field, covering most of the studies up to 1951, was given by Jost.' More recent papers include those by Hoffman2 on self-diffusion in mercury, Morgan and Kitchener" and Stark, Shchilishchev, and Kazachkev4 on the diffusion of various elements in liquid iron, and Grace and Derge on the diffusion of bismuth in bismuth-lead alloys. The need for more experimental data to aid in the evaluation of existing theories prompted the

Jan 1, 1957

By Francis B. Foley

THE casting of steel in large molds brings into play all of the undesirable effects that result inevitably from slow cooling. The origin of the molten metal, whether basic or acid open hearth or electric furnace, has little if anything to do with the phenomena involved. If the quantity of molten metal to be cast in a single mold is large enough, there is very little one can do about it-the metal will cool so slowly that 'nothing one can do, other than to provide as good feeding as practicable from an adequate reservoir of metal in the sink head, will be of any avail. Recently we have had occasion to cast a 108-in. octagon ingot weighing 545,700 lb, necessitating the combining of metal from three 100-ton open-hearth heats. This is one of the largest ingots ever made. The body of the ingot weighed 448,800 lb, which includes a bottom pool of about 7500 lb of metal, and the sink-head weight was 96,900 lb, or about 18 pct of the total weight.

Jan 1, 1947

By I. R. Kramer

The apparent activation energy, U, JOY plastic deformation of aluminium, copper, and gold single crystals and polycrystalline aluminum was found to he dependent upon surface condition. At low strains, the value for U for aluminum single crystals was 4200 cal per mole ; however, this value decreased to 920 cal per mole when the specimens were polished during the test at a rate of 50 X 10-5 win-1 The activated volume also was found to increase with the rate of metal removal. That the surface plays an important role in plastic-deformation processes has been adequately demonstrated.1-4 Of particular interest at this time are the observations4 that the creep rate of single crystals of fee metals is increased markedly when specimens are polished during the deformation process. These observations were interpreted in terms of a dislocation debris layer at the surface regions of the crystal. This layer, which appears to be a region containing a high concentration of dislocations or segments of dislocations, not only will impede the egress of dislocations on the primary slip system, but will also provide a barrier against which dislocations may pile up. By this means, a stress which opposes the motion of dislocations will be generated. It is considered that this stress must be taken into account in any theory which describes the plastic-deformation process. Although a detailed dislocation model cannot be given at this time, it may be stated that the stresses opposing the motion of dislocations arise from the dislocations in the debris layer, Ts, and ti due to the resistance to motion imposed by internal obstacles such as Lomer-Cottrell barriers, subgrain and grain boundaries, forest dislocations, and so forth, as well as the resistance due to the presence of jogs on dislocations and the interaction of the stress fields of dislocations, and so forth. In essence, we have added an additional term, ts, to the usual form of the equation T = Ta- Tb, where Tb is the back stress due to the various types of obstacles which impede the motion of dislocation. Accordingly, the net stress, t, acting on a dislocation may be written as where Ta is the applied shear stress. For deformation which occurs by a thermally activated process5,8 ?=Ae-u/kT = A e(u,-VT)/kT [2] and U = Uo- Vt PI where U = activation energy for plastic flow, y = shear strain rate, Uo = activated energy for plastic deformation in the absence of stress and depends upon the particular deformation process, V = activated volume, k = Boltzmann constant, T = temperature, OK, and A = frequency factor. From Eqs. [I] and [3], U = Uo- V(Ta - Ti - TS) [4] and it is seen that if Ts decreases, the activation energy, U, must decrease if V remains constant. However, as will be shown, V is a function of the surface conditions. In their work on aluminum, Lytton and coworkers7 reported that at low strains the activation energy was 3400 cal per mole and at high strains it was 28,000 cal per mole. The lower value was interpreted in terms of the energy necessary to overcome the Peierls force, while the higher value was associated with the energy necessary for dislocations to move by a cross-slip process. It will be shown that the lower activation energy is associated with the surface debris layer rather than with the Peierls force. EXPERIMENTAL PROCEDURE Single crystals having a nominal cross section of 1/8 in. and a 3-in. gage length were prepared by a modified Bridgman technique using a multiple-cavity graphite mold. The initial purity of the metals was 99.997, 99.999, and 99.999 pet for aluminum, copper, and gold, respectively. The orientation of the specimens is given in Fig. 1. The measurement of the activation energy as a

Jan 1, 1964

By Strathmore R. B. Cooke, Paul B. Queneau

The kinetics of the dissolution of scheelite in basic solutions of carbonate and fluoride were investigated. Work was also done with solutions of alkali metal chloride, hydroxide, phosphate, and mixtures of phosphate and fluoride. The study was conducted at 90 psig and at temperatures ranging from 100" to 155"C, and both natural and synthetic scheelite single crystals were used. The interaction of scheelite with carbonate solutions generally followed a parabolic rate law, and resulted in the formation of calcite crystals on the attached surface. The transport of the CO3 through the calcite to the scheelite surface was probably rate -controlling between 115" and 135°C. Positive deviations from Parabolic behavior were observed at 100" and 155?C, presumably due to the calcite grain growth, and to the formation of a noncoherent calcite layer, respectively. The leaching of scheelite with alkaline fluoride solution produced a calcium fluoride reaction-product which covered the surface as a sheet-like layer. Below 110°C the dissolution rate was parabolic; at 115" and 135°C it was linear. In the linear region, the periphery of the calcium fluoride layer lifted from the sample. Only the lower layers, braced by the scheelite substratum, remained unbroken. This bound layer, approximately constant in thickness, limited the rate at which the fluoride could attack the scheelite. The phosphate and phosphate-fluoride leaches dissolved scheelite at a linear rate; solid reaction products were respectively hydroxyapatite and fluorapatite. Sodium hydroxide and chloride were not effective leachants, and did not produce observable solid reaction products. THE feasibility of pressure leaching of scheelite pulps with basic solutions containing either carbonate or fluoride ions, as indicated by the following equations, has been established by previous investigators:1-3 200°C CaWO4s + CO37q - CaCO3s+WO4aq [1] 200°C CaWO4s + 2Faq ^ CaF2s+WO4aq [2] It is to be noted that a commercial process employing reaction [I] is in use at Union Carbide's operation near Bishop, Calif. In the earlier work referred to, it was apparent that the precipitation of the solid reaction-product on the scheelite particles sharply reduced contact of the leachant with the scheelite. We have extended this work by studying the kinetics of dissolution employing single crystals of scheelite of known exposed surface area. In addition, the effectiveness of solutions of phosphate, of phosphate with fluoride, and of chloride and hydroxide as leachants for scheelite have been investigated. EXPERIMENTAL Apparatus. The low-pressure autoclave used in this wo (100 psig maximum) is essentially that of J. Halpern4 as modified by F. A. Forward.5 Constructed entirely of 316 stainless steel, its maximum capacity is 4000 ml. The temperature in the autoclave was regulated to *0.5?C by a Wheelco thermocouple controller. A 4-in. diam, three-bladed impeller, circulated solution upward against the sample, and a strobo-scope permitted holding the stirring rate to *15 rpm. A check valve and a "pop" type safety valve were installed, a sample holder was fixed to an externally adjustable rod, and a water-cooled condenser was placed in series with the sampling valve. The stainless steel sample holder, Fig. 1, held the epoxy-mounted sample (f) five mm above the impeller. Tightening the tapered sleeve (d) positioned the epoxy-resin specimen-mount by forcing it back against the spacer (c). The mount (e) was 1 in. diam. Sample Description and Preparation. Both synthetic and natural scheelite crystals were leached. The former were single crystals of 99.95 pct purity which were leached approximately perpendicular to the "c" axis; they were supplied by the Gallard-Schlesinger Chemical Manufacturing Corp. The natural crystals, supplied by Minerals Unlimited, were transparent, analyzed 99.8 pct CaWO4, and in ultraviolet illumination exhibited the characteristic blue glow of substantially molybdenum-free scheelite. To permit exposure of an essentially constant surface area of scheelite to the leachant, the samples were mounted in Scotchcast Brand Resin No. 250 (Minnesota Mining and Manufacturing Co.). The mount-

Jan 1, 1970

By G. K. Engelhart

A multi-stage counterflow process developed in Germany preheats dry pulverized portland cement raw materials held in suspension in rotary kiln waste gases. Capacity of the first kiln installed for this purpose in the United States has been increased from 860 to 1500 bbl per day, with fuel reductions from 1,100,000 Btu to 650,000 or 700,000 Btu per bbl. Sixty percent of total waste gas is used. As full use of the gas stream is approached, additional kiln production and fuel economy may be expected. EFFECTIVE use of rotary kiln waste gases to preheat dry pulverized materials has been demonstrated in full-scale operation at the Allentown Portland Cement Co. plant, Evansville, Pa. Pulverized raw materials are preheated in suspension in the gas stream in a multi-stage counterflow process which draws the gases through a series of cyclone collectors. Upon entering the first cyclone stage the material, continuously delivered and suspended in the gas stream, is successively collected and re-suspended until it discharges through the kiln feed pipe. Gas and material contact time is thus prolonged, providing a high degree of heat recuperation with a very low temperature differential between gas and material at the final stage. The suspension preheater, developed by Klock-ner-Humboldt-Deutz AG of Cologne, Germany, was first installed at the Norddeutsche Huette plant, Oslebshausen, Germany. Similar preheaters are now in operation at three other German cement plants. The first American installation, at the Allentown Portland Cement Co. plant, was designed and manufactured by Fuller Co. of Catasauqua, Pa., Humboldt's licensee for the United States, Canada, and Mexico. Design of this installation is essentially the same as the German original, but provision was made for varying the method to adapt the process to specific objectives of American portland cement production. Differences between German and American cement clinker production practices are directly related to differences in three primary production cost items: fuel, labor, and power. Because fuel costs are high in Germany and elsewhere in Europe, thermal efficiency has been the first objective of European cement producers and manufacturers of rotary kilns. The Germans have developed such recuperative equipment as the present suspension preheater, the Miag calcinator, and the Lepol kiln, the invention of 0. G. Lellep. In North America labor is the principal cost item, although rising fuel costs are of growing concern. High clinker production is therefore of first importance. Recent installations of longer dry process cement kilns have been disappointing, failing to make satisfactory reductions in exit gas temperatures when production is held at an acceptable level. The Humboldt suspension preheater satisfies both

Jan 1, 1955

By P. D. Frost, H. A. Robinson, J. R. Doig, M. W. Mote

The mechanism of hardening in heat-treatable zirconium alloys was foUNd to be analogous to that for titanium alloys. Zirconium containing a relatively large addition of a ß -stabilizing element such as molybdenum or columbium can be hardened by the following transformation: Lean alloys, having insufficient alloy content to retain ß at room temperature are hardened by the following transformation: Application of these findings in Zr-Mo-Sn and Zr-Nb-Sn alloys produced strengths as high as 190,000 psi with reasonable ductility. PRIOR research on zirconium alloys has been concerned with development of greater strengths and creep resistance by solid-solution hardening or by dispersion hardening. Although solution and aging heat treatments had been applied earlier to zirconium alloys, quenching frequently produced low ductility. The possibility that the ß-to-w transformation, discovered earlier in titanium alloys,' might also occur in zirconium alloys and cause low ductility was considered, and, indeed, was found as predicted2 to be the case. In the earliest experiments, the heat-treatment response of titanium, too, was disappointing. However, by avoiding the formation of the embrittling w phase, it became practical to obtain room-temperature strengths higher than 180,000 psi, with elongation values of 10 pct.3 Based on the present concept of titanium heat treatment, the principal requirement for a heat-treatable zirconium alloy is that it contains a certain minimum amount of one or more ß -stabilizing elements. Only molybdenum, columbium, and tantalum, when present in sufficient amounts, are known to stabilize ß zirconium to room temperature during rapid cooling from the ß field. Tantalum was undesirable because of its high thermal-neutron cross section. Aluminum and tin are effective a stabilizers, but aluminum has been shown to seriously decrease the corrosion resistance of simple zirconium alloys in hot water. Therefore, for the present study, tin was used as the stabilizer addition. The alloys selected for this evaluation are presented in Table 1 along with their analyses and ß-transus temperatures. The analyses indicated that intended compositions were usually realized. EXPERIMENTAL PROCEDURES All of the alloys were melted from sponge zirconium and fabricated to sheet for heat treatment

Jan 1, 1960

Equilibrium in Lead Smelting. By S FREDERICK RAVITZ AND KENNETH E FISHER (Tech Pub 681, also Trans , vol 121 2300 words) Four liquids are ordinarily produced in lead smelting, namely, bullion, speiss, matte and slag To determine whether these exist together in equilibrium, the distribution of gold and silver among them was measured To crucibles containing similar mixtures of all four products, varying amounts of silver were added, and the crucibles were heated together under the same conditions for 3 hr, during which the charges melted and separated into four layers After cooling, these layers were assayed for silver, and the distribution coefficients, 1 e , the ratios of the concentration of silver in any particular layer to that in the bullion, were calculated In each experiment, each distribution coefficient was found to be constant, regardless of the amount of silver used Similar results were obtained using gold instead of silver The constancy of the distribution coefficients indicates that the bullion, speiss, matte, and slag exist together in equilibrium

Jan 1, 1937

By Jouko O. Kallioinen

The control of zinc flotation at Outokumpu Oy's Pyhasalmi and Vihanti mines is described. At Pyhäsalmi the zinc flotation circuit is partially open. Zinc and other metal assays of pulp flows are measured and direct assay control of concentrates in various flotation steps is adopted. Assay control is carried out by adjusting flotation air and pulp levels. Optimization with copper sulphate ensures high Zn- recovery and minimum copper sulphate consumption. A froth depth monitor is used to measure froth quality. At Vihanti the zinc flotation takes place in closed circuit. The most important control loop is the Zn-assay control of rougher concentrate by adjusting flotation air. The quality of froth is measured indirectly and thus copper sulphate consumption is altered. The circulating load is controlled also by flotation air in the three cleaning steps. The comparison of the control strategies shows that a more sophisticated control is adopted at Pyhäsalmi because the selective flotation of this massive sulphide ore is considered to be difficult. The control strategy includes numerous tests performed by the computer and control algorithms developed for the case. The control targets of the two zinc flotations described are also different: At Pyhäsalmi Zn-assay control of final concentrate including copper sulphate optimizing, at Vihanti the control of circulating load and Zn-assay of rougher concentrate.

Jan 1, 1984

By L. A. Rapport, J. R. McCord, W. P. Drews, K. H. Coats

Water movement about an oil or gas reservoir can be predicted provided an aquifer influence function is known. This function is generally determined from an electric analyzer study or by fitting an idealized mathematical model to field data. A prohlem arises in determining that influence function which best reproduces field data and satisfies certain smoothness requirements, without making any idealizations concerning aquifer geometry and heterogeneity. This study shows the problem to be solvable through the linear programming technique and presents applications to one oil reservoir and two gas storage reservoirs. In addition, a theorem is stated and proven which confirms influence junction smoothness requirements heretofore accepted on physical intuition and establishes additiotzal smoothness constraints formerly not recognized. INTRODUCTION The pressure decline accompanying production results in water encroachment into oil and gas reservoirs situated adjacent to aquifers. The importance of this water movement derives from the significant dependence of production rate upon reservoir pressure and of pressure, in turn, upon water encroachment. Pressure and rate of water movement are uniquely related through an "influence" function which may be in the form of reservoir pressure response to a unit water encroachment rate or of water movement caused by a unit reservoir pressure drop. This influence function reflects the heterogeneity and geometry of the aquifer and is therefore particular to each reservoir. If the influence function is known, then reservoir pressure may be predicted from a production rate schedule, or vice-versa, with the aid of the material balance equation which relates water influx to reservoir production and pressure. The problem of determining this influence function for a given reservoir has been approached in three different ways. Van Everdingen and Hurst calculated and tabulated certain influence functions pertinent to idealized mathematical models which satisfy simplifying assumptions such as aquifer homogeneity and elementary reservoir-aquifer geometries.' Other studies developed additional tables for a variety of elementary reservoir-aquifer geometrical con- figurations and demonstrated their validity and utility.:' Hicks, et al. described the use of an electrical network to determine an influence function giving "best" match of field history and allowing prediction of future performance.' Finally, Hutchinson and Sikora5 and Katz, Tek and Jones attempted to develop a calculation method for deriving the influence function directly from field data with no idealizing assumptions concerning aquifer geometry and homogeneity. They encountered difficulties with inaccuracies in field data and with satisfaction of well-known smoothness requirements of the influence function. This study is concerned with the determination of influence functions from field data and, more specifically, treats the following problem: given field pressure-production data of arbitrary accuracy, how does one determine the influence function which, subject to satisfaction of known smoothness requirements, gives best agreement with field history? A rigorous solution to this problem is ohtained through linear programming as described below. Example applications to one oil and two gas storage reservoirs are presented. In addition, a theorem is proved which confirms influence function smoothness requirements heretofore accepted on physical intuition and establishes additional smoothness requirements formerly not recognized.

Jan 1, 1965

By M. H. Richman, L. M. Markowitz

MUCH of the available information on which the heat treatments of a particular steel are based is found in the isothermal-transformation diagram. Such is the case despite the fact that the usual thermal treatments involve continuous transformations, i.e., transformations which occur on cooling, rather than isothermal transformations. This rather unusual practice is continued because of the abundance of published isothermal-transformation diagrams1, 2 which are relatively easy to determine experimentally as compared to continuous-transformation diagrams.3, 4 However, this can easily lead to the production of improper micro-structures and may not allow full advantage to be taken of the inherent hardenability of a steel. A mathematical method of estimating the continuous-transformation diagram from the available isothermal data was developed by Grange and Kiefer;5 but, due to the mathematical approximations required in the calculations, the computation of continuous-transformation diagrams has been limited to individual cases and no large-scale compilation of these diagrams is available. With the present availability of high-speed digital computers, the problem of time-consuming approximations may be minimized and continuous-transformation diagrams may be constructed with the insertion of isothermal data into a basic program. It is the purpose of this report to announce the availability of such a program and compare the computed and experimental continuous-transformation diagrams for two different steels. Let us first review the method of Grange and Kiefer5 and then compare the results of the machine calculations with the experimentally determined diagrams. In order to apply this method, one requires the isothermal-transformation diagram and a set of curves representing cooling at constant rates. A section of an isothermal-transformation diagram is shown in Fig. 1 together with a cooling curve of M0F per sec. The cooling curve is constructed to start from the A1 (eutectoid) temperature if the transformation product is the eutectoid microconstituent (i.e., pearlite or bainite), from the A3 temperature if the product is primary ferrite, or from the 4, if it is proeutec-toid cementite. The cooling curve in Fig. 1 intersects the curve representing the start of isothermal transformation at a point A' corresponding to a temperature TX and a time fX. An arbitrary lower temperature To (on the

Jan 1, 1968

By J. W. Spretnak, G. W. Cunningham

A study has been made of the growth and disappearance of voids in the interface of pressure bonded copper. The formation of visible voids is primarily due to spheroidization and coalesence of microvoids produced during the application of pressure. The microvoids could be prevented from forming by the application of high pressures or by increasing the ductility of the copper. Migrating grain boundaries were found to be more effective in void removal, than stationary grain boundaries. DURING the course of an investigation on the mechanism of pressure bonding, it was found that voids formed in the bonding interface which inhibited migration of the interfacial boundary and grain boundaries in the bond region. Therefore, an effort was made to determine the nature of the voids and how they form, grow, and disappear. This paper reports the results of such an investigation. The existence of interfacial voids is not solely a characteristic of massive components of metal which have been bonded by the application of heat and pressure, but is a phenomenon which has been observed in sintering as well. Simonsen attempted to study the sintering process by hot-stage microscopy and thereupon observed the formation of interparticle porosity as sintering proceeded. It was assumed that the porosity was due to grooves created at the location where grain boundaries joined the surface of the particle. Pranatis, Castelman, and seigle2 have also observed voids along the areas of contact in wound-wire specimens used for sintering studies. They did not discuss the point in detail since this behavior was not general, but they did suggest that the voids might develop as a result of stresses along the interparticle contact area. In previous investigations on pressure bonding, workers3 have suggested that voids may exist in the region where mating surfaces are placed in intimate contact, but the existence of the voids was not verified and no attempt was made to study the growth and disappearance of these voids. Durst noted the existence of pores in roll-clad structures prepared by cold reducing two sheets to force them in contact and then annealing to improve the bond. Since his unbonded regions contained a gas which he assumed to be insoluble, he proposed a mechanism which consisted of spheroidization of the unbonded regions and a growth of the contact area, but no speculations were made regarding disappearance of the gas filled pores. One interesting comment made by Durst was the suggestion that flattened voids with sharp corners which are produced during roll bonding will have a greater driving force for spheroidization than the more rounded pores created by pressing metal powders and thus spheroidization and neck growth will occur at lower temperatures. In this study it was necessary to demonstrate conclusively that voids can actually exist in the interfacial bond area. Experimental work was then directed toward a study of the mechanism whereby the voids grow and subsequently disappear.

Jan 1, 1963