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By J. H. Smith, H. W. Paxton

ALTHOUGH many structural and kinetic investigations have been made for alloys of iron and nickel, only meager data exist from thermodynamic investigations. The purpose of this note is to estimate the free energy of the Fe-Ni solid solutions from thermodynamic data available for ternary alloys containing iron and nickel. The lack of a description of the thermodynamic behavior for the Fe-Ni system has required the structural and kinetic analyses of the system to assume some form of solution behavior, usually regular, e.g., the mar-tensite transformation analysis of Kaufman and Cohen, 1 consistent with the limited thermodynamic data. Indications that this system could exhibit ideal solution departures might have been suggested by the large deviations from additivity rules observed in the density and lattice-parameter measurements of Jette and Foote2 who interpreted this in terms of possible solute-solvent interactions. Later Turkdogan et al. 3 and more recently Ward and wright 4 found a minimum in the graphite solubility in liquid Fe-Ni solutions near the concentration of FeNi3 with deviations from linearity persisting at all concentrations. This was interpreted by Ward and wright4 to indicate negative heats of solution and was suggestive of short-range ordering. The infinitely dilute activity coefficient of carbon (?oC) was also observed by smith5 to pass through a maximum near the FeNi3 concentration in Fe-Ni solid solutions. Recent investigations of the liquid solutions over the entire concentration range by Zellars et a1.' and Speiser et a1.," using vapor-pressure determinations, revealed both negative departures from Raoult's law and a nonregular solution behavior. The solid alloys have been studied by Oriani 8 and Kubaschew-ski and von Goldbeck6 employing gaseous H2/H2O equilibria with Fe and FeO. Both investigations were in substantial agreement, indicating very small departures from ideality. However, Oriani observed the formation of Fe3O4 (instead of FeO) at XFe= 0.441 which severed the equilibrium and precluded experimental investigation of the nickel-rich alloys. Heat-capacity and heat-content measurements have been evaluated by Montgomery10 and found generally unsatisfactory for gleaning thermodynamic information. This is due to the unknown final states of the alloys caused by the interference of the martensite transformation on cooling iron-rich concentrations and superlattice formation, magnetic transformation, and the varied heat treatments used by investigators of nickel-rich concentrations. As an alternative to the experimental difficulties, indirect estimates of the solid-solution behavior have been made by Fleischer and Elliott11 and Smith et a1.12 From their measurements of the solubility of Fe-Ni alloys in liquid lead, Fleischer and Elliott calculated the nickel activity (aNi) (and integrated for aFe) by assuming: 1) liquid lead has no solubility in solid Fe-Ni alloys, 2) Henry's law is obeyed throughout the liquid lead-rich phase (0— 12 at. pct Nil, and 3) Henry's law constant is independent of relative iron and nickel concentrations. The estimate of Smith et a1.12 was obtained

Jan 1, 1964

By C. D. Rugen

Ground raw material as fed to the cement kiln generally is a mixture of two to four components, each of which may have widely varying physical and grinda-bility characteristics. Chemically similar materials found in the same or different deposits may also differ appreciably in physical properties, depending on their crystalline structure. The calcareous or principal cement raw material may vary from a soft chalky limestone or friable cement rock at one plant to a hard limestone or oyster shell at another plant. Argillaceous materials include clays, shales and granulated slag. Siliceous and/or iron-bearing material, including sand, 'iron ore and cinders, may also be required in addition for certain types of mixes. Frequently differences in grindability characteristics are not given the attention they deserve in comparing grinding results at one plant with those at another or in selecting suitable circuits or equipment. Many types of crushing and grinding units are used, with numerous open and closed circuit arrangements. Both wet and dry processes are used successfully. When rebuilding or installing a new grinding department, the choice of process or circuit in some cases may be dictated by the nature of the materials being ground but in other cases it may be the result of good salesmanship or a compromise. An over-all evaluation of wet process vs. dry process grinding should not be made without considering the effects on all other *producing departments in the plant. In general, the more recent grinding installations, both wet and dry, have employed closed circuits, but many older open circuits are still in successful operation. In our experience, closed-circuit raw grinding pays, because of lower power consumption and less operating labor per ton of product. However, some dry open-circuit mills with improved equipment and operating methods compare favorably in performance with dry closed-circuit units. Character of Ground Raw Mix (Kiln Feed) Grinding in the cement plant in general requires a considerably finer product than in most ore-grinding operations. A distinction between fineness of kiln feed and of cement may be made in that kiln feed preferably should be ground to a limiting size,whereas finished cement should include a range of size fractions including sufficient fine flours to give a product with satisfactory physical qualities. Grinding raw mix for kiln feed therefore is more comparable to ore grinding, although the limiting size is smaller. Most kiln feeds are ground from 85 to 95 per cent passing 200-mesh, depending on mix composition. Some cement chemists believe that raw materials cannot be too fine, since her particles theoretically combine more readily and intimately in the kiln. However, there are certain definite practical objections to extremely he kiln feed, such as loss of kiln dust, unstable material flow through the kiln and greater difficulty in control of chemical composition due to dust loss, and the disproportion of fines from the more easily ground component. Our

Jan 1, 1948

By F. N. Rhines

Sintering may be defined as the process by which powders bond themselves into coherent bodies, usually, although not necessarily, under the influence of pressure and elevated temperature. For the sake of clarity and simplicity, the present survey will exclude from consideration the sintering of mixed or alloyed powders, with attendant complications, but at the risk of overlooking information of general applicability. Sintering in the presence of a liquid phase is thus automatically eliminated. The sintering of alloys involves much additional subject matter and deserves separate consideration. Since the literature of the subject is extensive and widely scattered, it will not be feasible to consider the contributions individually. Instead, the subject matter will be classified according to experimental observations and theory, and will be presented in summary form. It should be noted that the appended list of references does not constitute a complete bibliography; it includes only those works quoted below. More extensive bibliographies are included in several of the references; see particularly references 7, 9, 28, 34, 38, 50, 52, 54, a "Bibliography on Powder Metallurgy" published by the Library of Congress and a pamphlet published by the Metals Disintegrating Co. entitled "The Field of Powder Metallurgy and Bibliography." 11. Summary of Experimental Observations The following classified list is composed of general statements of established fact derived from the experimental results reported in the published literature. A few contested observations are included, because of their potential importance; these are labeled as such. Any satisfactory and complete theory must be capable of explaining all of the uncontested facts. Obviously, some important facts may be missing from this list and these may hold the key to the correct explanation of the sintering process, but the possible lack of such material should not deter attempts to understand the subject on the basis of what is available here. A, The Initial Bond at Room Temperature a. To a limited extent uncompressed powders and massive metals adhere at room temperature. Clean tin powder forms a weak "cake" on standing at room temperature, the strength increasing with time. Clean gold surfaces adhere on light con-tact, as do those of many other substances, including nickel.27 b. Upon compression the strength of the bond- is increased progres-ivelv. There is a limit of pressure

Jan 1, 1946

A Discussion at a meeting of the New York Section, Dec. 2, 1914 D. H. BROWNE.-If 35 years ago we had met to discuss the subject that is before us to-night, the criticism that we must all be mad or we would not be here at all would have been perfectly applicable. No group of men would have come together a generation ago to discuss the subject of smelting ores without extraneous fuel, or largely by the oxidation of their own impurities, without incurring the imputation of being crazy. But metallurgy, like all other branches of human industry, progresses by idealism. In every generation there are old men who see visions and young men who dream dreams. Thirty-five years ago John Hollway conceived the idea that in the Rio Tinto ore the sulphur and iron, if properly oxidized, could be made to produce heat enough to carry on the smelting of the ores. He saw the vision. Twenty-five years ago Mr. Austin, of Montana, took out a patent on a furnace in which to carry out Hollway's ideas. He dreamed the dream. Twenty years ago a man working in Montana grasped the possibilities of this idea. To him has been given that inexpressible pleasure which comes from realizing the idea and making the concept concrete. Gentlemen, it gives me great pleasure to introduce to you the man who made the ideal real, Robert Sticht, of Tasmania. ROBERT C. STICHT, Queenstown, Tasmania.-I find it extremely difficult to act up, in the smallest degree, to the enconium passed upon me by Mr. Browne. It is true it has been my good fortune to be able to put some sort of method into the "madness" of 25 years ago; but I am not the originator of the idea, nor the only one who has carried it out. Mr. Browne mentioned the originator, who undoubtedly is Mr. Hollway. He also mentioned Mr. Austin, who gave the first instigation to pyrite smelting as now practiced. As against both of these men I was fortunate enough to be able to command the necessary natural resources to carry out the idea continuously in a practical way, so as to make it permanently possible.

Jan 4, 1915

By R. T. Webber, R. B. Owen

The vapor phase deposition of molybdenum and tungsten from the hexacar-bonyls has been thoroughly investigated by Lander and Germerl, and shown to yield well-bonded coatings on a variety of hot metallic surfaces. They also demonstrated that chromium coatings2'3 could be similarly deposited, but did not investigate this metal extensively. Recently, conditions have been described by which this compound can be prepared in quantities sufficient for laboratory scale plating experiments, and it is the purpose of the present communication to outline the results of preliminary experiments upon the plating of chromium from its carbonyl. Apparatus and Technique The apparatus used in these experiments is shown in Fig I. At one end, connected by a short length of rubber tubing, is a Cenco Hypervac 20 pumping continuously. At the opposite end is a needle valve which allows a small stream of purified hydrogen to flow through the apparatus. Connected in series are a trap T1, maintained at the temperature of dry ice and acetone, the plating chamber, and two traps T² and T3 containing crystals of the carbonyl. T² is kept in a constant temperature bath (not shown), while T³ is at room temperature. Stopcock S6 allows the hydrogen flow to by-pass the carbonyl traps. A McLeod gauge is connected so that it can measure the pressure at the pump through Se, or the pressure at the plating chamber through S9 and S6. The standard (12 liter) volume connected by Sb is used to determine the volume included by S4, S6, SB, Slot the needle valve and the McLeod gauge. Knowledge of this volume allows calibration of the flow of hydrogen. The apparatus* is built entirely of pyrex, except for the needle valve, the rubber connection to the Hypervac, and the cover of the plating chamber. The plating chamber is water-jacketed, with a large brass top allowing insertion of the specimen to be plated. Set into the brass top is a ground glass stopper through which thermocouple leads are sealed. The thermocouple wires (pure Pt, and 87 pct Pt-13 pct Rh) serve the double purpose of measuring the specimen temperature and suspending it in the chamber. Surrounding the chamber is the coil of an induction heater, H. The apparatus is designed to allow variation of the following conditions: (I) the specimen temperature, from room temperature to about 1000°C, (2) the carbonyl vapor pressure, from 40 to 220 microns, and (3) the hydrogen flow. In several runs, 0.8 to 1.8 PCt of hydrogen sulfide was introuced through a needle valve that replaced S4. The vapor pressure of the carbonyl is

Jan 1, 1949

By J. D. Price, W. M. Bertholf

One of the chief difficulties with which the operator of a coal washing plant has been forced to contend is the handling of the very fine coal. First he has the problem of separating the fine coal from washery water. This is usually accomplished by the use of settling cones or Dorr thickeners: in either event the separated fine coal contains a high amount (40 to 80 pct) of water and, somewhat loosely, dependent upon the size of the coal particles present, may be known as sludge or slurry. His second problem is the satisfactory further dewatering of such separated sludge and/or slurry. At the coal washing plant of the Colorado Fuel and Iron Corp., washed coal from the Deister Plat-O tables is sluiced to a stationary inclined de-watering screen provided with 3/16 by 1-in. slots, and the coarse coal passing over this screen is conveyed by a Baum-type elevator and a flight-type distributing conveyor to a battery of Carpenter centrifugal driers. The fine coal and water passing through the openings of the primary dewatering screens, plus the fine coal passing through the screens of the centrifugal driers (and no small portion of which is the result of the disintegrating action of these driers) is pumped to two 30-ft Link Belt settling cones. The sludge recovered as underflow from these cones was formerly dewatered on stationary screens having 1/16 by 1-in. slots and discharged on top of the coarse washed coal in the Baum drainage conveyor; but after a relatively few hours of op eration the circulating load of fine coal on this conveyor built up to a point where it became necessary to reduce the quantity of feed to the washing tables. The original arrangement of our coal washing and dewatering equipment is shown in Fig 1. In order to regain the loss in active throughput which had been caused by this circulating load, an installation of six vibrating filters was made during the year of 1936. This resulted in an increase in normal tonnage of washed coal from 1430 to 1750 tons per 8-hr shift, a gain of slightly over 22 pct. This increase in throughput has made a very substantial decrease in the " conversion cost" per ton of washed coal. Since the vibrators were installed, we have gained about 2,000,000 tons in production, compared to what would have been produced in the same number of shifts at the former rate. Putting it in slightly different form, we have saved in the past 12 yr the cost of 1400 operating shifts in the washery. Fig 2 shows the location of the vibrating filters as applied to the original flowsheet. It will be noted that the sludge from the bottom of the settling cones is passed through a distributing box and thence to the filters. The de-watered coal from the filters is de-livered to the conveyor receiving the dried coal from the Carpenter driers.

Jan 1, 1950

By Heinrich Ries

Jan 1, 1907

By Mohamed Mortada

A practical analytical method is developed in this paper which provides the practicing reservoir engineer with a handy method for analyzing oilfield interference problems. The procedure employed entails the principle of superposition of individual eflects. A set of charts has been developed and can be used to evaluate the individual effects. The charts represent non-steady state pressure distribution in an extensive aquifer due to a constant rate of production from an oilfield which can be approximated by circular geometry; they are constructed from solutions to the diffusivity equation considering a circular sink as distinguished from a point sink. The solutions are obtained partially from mathenlatical considerations and partially from analog and digital computations. By virtue of the method of images, the charts can be used also to treat the case of production near a fault. In addition, provisions are made for treating oil fields, which are produced by partial water-drive. Treating an actual field case is deferred to a subyequent writing; however, illustrative example is presented to demonstrate the method of application. The pressure distribution in linear and limited radial aquifers is currently under study. INTRODUCTION With the increasing difficulty of discovering new oil reserves, attention is necessarily focused on the efficient development and production of existing reservoirs. Efficient production depends on the availability of reliable means for predicting the pressure-production behavior of oil fields. The prediction is usually performed by analytical methods or computers. Analytical methods are often limited to systems which can be approximated by simple geometry. However, analytical methods have the distinct advantage of being readily performed without special equipment. Analog and digital computers lend themselves to a variety of problems, but are not always locally available and consequently their use is limited. One particular situation in which analytical techniques are needed involves studies of multiple, water-drive oil fields sharing a common aquifer. Such oil fields are in hydrodynamic communication. Therefore, production from any of the oil fields is accompanied by a pressure decline which is transmitted through the aquifer to the other oil fields and manifested as pressure interference. The rate of propagation of the pressure decline is such that the pressure may be significantly reduced many miles away from a producing pool. An example of pressure interference is found in the Woodbine formation in East Texas. There. a dozen or more pools, including several of major size, draw on the Woodbine formation for water drive. The pressure in the water-bearing portion of the formation has been significantly reduced over an area of several thousand square miles. This reduction of pressure has been such that when the Hawkins pool was discovered in 1940, the pressure in it had already been reduced 280 psi below the initial value in the aquifer. This resulted from prior production from other Woodbine sand pools, including, in particular, the East Texas field some 20 miles to the east of Hawkins.' The above example indicates that the interference effect can be significant and should be taken into con-

Jan 1, 1956

By J. M. Pilcher

The application of oil to coal for-the reduction of dust has greatly increased the consumers' satisfaction with solid fuels, especially those for domestic use. The combination of oil-treated coal and automatic firing by a small stoker has made possible clean, automatic heating with bituminous coal. This, with the added pressure of competition by other fuels, has caused a rapid development of oil treating practice. A variety of materials derived" from petroleum oils is available from which one may choose for treating a par-ticular coal. Until recently, however, little information had been published to guide the choice. It is most im-portant that the proper type and amount of oil be used in order that all coals marketed as "dustless" will be reason-ably dustless, and thereby maintain a good reputation for oil-treatment. During the past two and one-half years, an investigation of a number of the problems related to the treatment of coal with oil has been conducted at Battelle Memorial Institute. This project was jointly sponsored by Bituminous Coal Research. Inc., Standard Oil Company of New Jersey, Sun Oil Company, and Viking Manufacturing Company. A progress report giving the principal results of the work of the first year was presented before the American Society of Mechanical Engineers in December 1937.1 The present paper is a summary of the entire inves-tigation.

Jan 1, 1939

By A. H. Shoemaker

THE shutdown of Homestake by Government order L-208, with its consequent disruption of a very stable and trained working force, coupled with postwar inflation and the coincidence that a mining depth had been reached that posed problems of ventilation, access to exploration areas, and choice of mining methods that would be applicable to zones of greater rock pressures made a very searching analysis of every phase of Homestake's operations a necessity. Any changes to be made had not only to meet the problems of deeper mining but also had to provide greater efficiency so that the mine might operate at a substantial profit until such time as a gold price adjustment might be forthcoming that would offset post-1945 inflation. Geology and Mining Situation The Homestake mine lies in the northern Black Hills in an area of Pre-Cambrian rocks exposed by the erosion of the paleozoic formations which covered the Black Hills. The Pre-Cambrian rocks in the vicinity of Lead comprise metamorphosed sediments with a total thickness of about 20,000 ft. The oldest formation, the Poorman, is ankeritic carbonate schist. The next oldest, the Homestake formation, host rock for all Homestake orebodies, is a siliceous iron-magnesium carbonate schist. The younger formations are dom-inantly argillaceous with some quartzites. Tertiary intrusive rocks cut all formations. The Pre-Cambrian rocks have undergone extreme isoclinal folding. Superimposed on this intricate folding are zones of shear folding which cross the isoclinal folds at small angles. The Homestake orebodies are pipelike replacements of the Pre-Cambrian Homestake formation where certain cross folds intersect some earlier isoclinal folds. These orebodies plunge flatly to the southeast at variable angles locally as steep as 45". The orebodies are replacement areas where numerous vein quartz of irregular shape have formed with surrounding zones of chlorite alterations containing disseminated sulfides and metallic gold. Where the numerous individual quartz veins with the sulfide and gold-bearing alteration zones are close together, large irregular orebodies with a roughly elliptical plan outline result. These ore zones may be more than 200 ft wide and 700 ft long in plan area. They have followed down the plunge of certain severely folded structures with great persistence. Two vertical operating shafts, the Ross and Yates, serve the mine, one with rope capacity to reach the 4850 level, the other to the 5000 level.

Jan 1, 1959

By Henry S. Drinker

The Musconetcong tunnel is situated in New Jersey, near the line of the Central Railroad of New Jersey, about twelve miles from Easton, on the Easton and Amboy Railroad, the latter being the extension of the Lehigh Valley Railroad to tide-water. Up to the present time, the terminus of the Lehigh Valley Railroad has been at Phillipsburg, N. J., opposite Easton, passengers connecting there with New York by the Morris and Essex (D. L. and W.) and New Jersey Central lines; freight and coal being forwarded by the Morris and Essex to tide-water at Hoboken, and by the Central Railroad to Elizabethport and Port Johnson ; also, by the Belvidere and Delaware connections through Trenton to South Amboy.

By O?Harra B. M.

THE work here described had for its purpose the procuring of data from which some quantitative estimate might be made of the results obtainable by using oxygen-enriched air in roasting zinc ores on a commercial scale. The principal metallurgical advantages of using enriched air in roasting zinc ores would be: 1. The rate of roasting would be increased, with consequent gain in the capacity of the roasting furnace. 2. As less air would be required for roasting, the volume of hot gases leaving the furnace and the heat carried out of the furnace as sensible heat in these gases would be less per ton of ore roasted; partly for this reason and partly because of the increased quantity of heat generated in the furnace by the larger amount of ore that could be roasted, the consumption of fuel by the furnace would be lessened; and by the use of air sufficiently enriched with oxygen the necessity of using fuel might be entirely obviated. 3. Roaster gas having a higher SO2 content could be produced; this would make possible greater capacity and more economical operation of the sulfuric-acid plant. Certain phases of the application of enriched air to roasting can be worked out only by experimenting with a furnace of commercial, or at least semicommercial, size. Thus the precautions necessary to secure proper. distribution of heat in the furnace;1 the volume of enriched air; and the proportion of oxygen in this air, necessary to give the desired increase in roasting capacity of the furnace and in SO2 content of the roaster gases;; and the most desirable frequency of raking, thickness of

Jan 11, 1924

By Marion Rice

THE copper-mining district of Jerome, Ariz., is of such economic importance that the following brief notes may be of interest. The ore deposits are said by Ransome1 to be pre-Cambrian, and are contained in the pre-Cambrian schists of the region. In the vicinity of the mine (the United Verde) the schist stands nearly vertical .and strikes a little west of north. At least three varieties are distinguishable-(1) a green rock, schistose, on its margins but grading into massive material, which is evidently an altered dioritic intrusive; (2) a rough gray schist with abundant pheno-crysts of quartz, apparently an altered rhyolite; and (3) a satiny, greenish gray, very fissile sericitic schist that may be a metamorphosed sediment. The ore occurs in varieties (2) and (3), the main belt of dioritic rock (1) lying just west of the orebodies. The ore is said to follow as a rule the layers of fine sericitic schist. T. A. Rickard2 says that the ore at the United. Verde Extension mine is found at the contact of diorite and schist, that both diorite and ore are earlier than the regional metamorphism, and that the quartz porphyry (" rhyolite" of Ransome) is of post-Cambrian age.

Jan 9, 1918

By David P. Hale

The Cartersville barite district is near Cartersville, Ga., in the southeastern part of Bartow County, about 43 miles northeast of Atlanta. The area over which active mining is being done extends about six miles in a northeasterly direction and is about three miles wide. Barite production in Georgia began about 1907,' but the existence of the mineral was known much earlier. At present four companies are operating washing plants and three other plants are operating on leases from those companies. The chief impurities in the ores are silica and iron oxide. The silica is easily washed and jigged out and gives little trouble. Any gravity separation between the iron and the barite is generally poor, owing to the slight difference in specific gravity. Two operators have turned to magnetic separation as the solution to the problem and have made remarkable improvements in the finished product. By very close sizing prior to jigging, the separation between iron and barite has been greatly improved. In some localities manganese occasionally appears as an impurity, but is fairly easy to eliminate by gravity methods. A considerable percentage of iron and silica is eliminated by being broken free in crushing. Until methods for the recovery of fine ore were introduced a minimum of crushing was done, but modern methods allow more than formerly. The depression years brought about the need for increased recovery of ore handled on the part of the producers and a demand for a higher grade of product on the part of the buyers. Improvements in milling and mining practice have had a far greater effect, however, than merely the production of a better grade of ore with greater recovery. They have opened for mining large areas that a few years ago were considered noncommercial deposits because of their inaccessibility and their high iron content. It is no exaggeration to say that the new methods have more than doubled present known reserves of barite ore of economic value.

Jan 1, 1942

By Thomas W. Dawson

The H. C. Frick Coke Co. has used belt conveyers for handling coal for the last eighteen years but, until recently, only for small tonnages and over short distances. The first installations were outside the mines for distributing coal to various parts of plants. A belt conveyer was put in service at Colonial No. 4 Mine in November, 1906, to carry coal from the main hoisting shaft to a storage bin serving two blocks of beehive ovens on the other side of the valley; it was in constant service until the Colonial No. 4 ovens were abandoned less than a year ago. This conveyor was in an overhead gallery that spanned our sidings and yard tracks and the main line of the Pennsylvania Railroad. It was a crude installation, from the viewpoint of present conveyor engineering practice. It had no mechanical feeding device, the coal simply ran through a gate in the side of a bin on to the belt; but one belt on this conveyor lasted eleven years. This conveyor is about 300 ft. long center to center of pulleys. It operated at a speed of 250 ft. 'per min-and carried about 400 tons per day. On this basis, the belt life of eleven years means that not over a million and a quarter tons was carried by the belt. whi1e: this is not a large tonnage, the cost per ton was much less than by any previous method in use for supplying coal to ovens located at a distance from the main shaft. The next belt conveyor was installed at Bridgeport Mine in 1907. It carried about the same daily tonnage as the first, delivering from the hoisting shaft to a coke-oven bin. Very few data were kept on this conveyor. It also operated until the coke ovens at the plant were put out of blast and the coal taken to the Clairton byproduct plant by river. In 1916, work was started to equip the Bridgeport, Palmer, Gates, and Ronco mines to load their entire output on the river for transportation to the Clairton byproduct plant, which was then being built. These mines were all operating at that time and had a large area of coal available for river shipment. The Monongahela Railroad was located between the hoisting shaft and the river at each of these plants and, therefore, had to be crossed at each location to deliver coal to the river. After careful study, it was decided to transport this coal from the hoisting shaft to the river at each of these plants by belt conveyors.

Jan 1, 1925

By M. T. Simnad, G. Derge, Ling Yang

STUDY of diffusion in molten substances is important in at least two respects. Diffusion data, combined with thermodynamic and kinetic information, throw light on the structure of the liquid state. Moreover, a knowledge of diffusion coefficients and their temperature dependence is useful in ascertaining the controlling step in many metallurgical reactions. Although diffusion measurements have been made on a number of molten salts, slags, metals, and alloys,'-'" the results available are still limited and widely scattered, especially for the high temperature melts. It is the purpose of this investigation to establish reliable procedures for the measurement of self-diffusion coefficients in high temperature melts and to use these procedures to determine the self-diffusion coefficients of iron in molten Fe-C alloys of different carbon contents. Experimental Measurement of self-diffusion coefficients in high temperature melts is usually carried out by using one of two methods. In the first, diffusion takes place between two cylindrical samples of the same material, one of which is made radioactive. The diffusion coefficient is calculated from the radioactivity penetration curve in the solidified sample after the diffusion. In the second method, samples contained in capillaries of an inert substance are immersed in an infinite reservoir of the same material. Either the material in the capillary or that in the reservoir is made radioactive and the diffusion coefficient is calculated from the change of the radioactivity of the sample in the capillary after the diffusion. The second method is simpler because a radioactivity penetration curve is not needed for the calculation of the diffusion coefficient; however,.it is valid only when no convection has occurred in the capillary during the diffusion. A radioactivity penetration curve is therefore always useful in indicating that the required conditions for the diffusion are ful- filled. Towers and Chipman" recently studied the self-diffusion of calcium and silicon in CaO-Al,O,-SiO, melts by using the capillary method. Instead of measuring the change of the radioactivity of the sample in the capillary, they autoradiographed the sample after the diffusion and calculated the diffusion coefficient from the intensity distribution of the autoradiograph. Their method is useful when the radioactive isotopes are weak ß-emitters, but is very difficult, if not impossible, to apply to cases involving strong ß or y-emitters. For such cases, sectioning of the sample according to the method of Morgan and Kitchener' may be used for the construction of the radioactivity penetration curve. The self-diffusion of iron in molten Fe-C alloys has been studied in this manner and the experimental procedures are described as follows: The diffusion apparatus is shown schematically in Fig. 1. The bath consisted of about 200 g of an Fe-C

Jan 1, 1957

By J. C. Febles

The use of iron for the precipitation of copper was known at least as early as the fifteenth century. Both Paracelsus and Basil Valentine refer to it in their writings, as early as 1500 A. D. It was used in Peru for this purpose prior to 1637, and at Rio Tinto, Spain, as early as the sixteenth century. The statement has been made repeatedly that in the early history of the mining industry at Butte, the practicability of this method of recovering copper from solution was overlooked, and that enormous quantities of copper-bearing water were allowed to go to waste, the copper in which might easily have been recovered at small cost; and that this oversight on the part of the mine operators was due to ignorance of this method of recovering copper. As a matter of fact, very little copper-bearing mineral was encountered in the mines of Butte until a depth of 400 or 500 ft. had been reached, and in many cases much greater depths were necessary to reach the copper-bearing zone. The water encountered in the upper levels (although in most cases quite highly mineralized) contained little or no copper, and it was only after considerable areas of copper-bearing ore had been uncovered and developed that copper sulphate began to appear in the mine water in any considerable quantity. In fact, the first water that was observed to contain copper carried it in such small amounts as to be of little or no importance. It was only after years of underground work had opened extensive areas of stopes, drifts, and other underground workings, these being subsequently filled with waste, nearly all of which contained small copper values, which became oxidized by exposure to the air and were acted upon by the slowly percolating mineral water, that the recovery of copper from mine water became commercially important.

Jan 1, 1914

By Nicholas J. Grant, Raymond E. Cairns

A high-purity chromium, made by solid-state extrusion, and a series of molten, extruded, dilute alloys containing carbon, oxygen, nitrogen, and sulfur were studied to establish the effects of composition, cooling rate, grain size, strain rate, and prior strain on the transition temperature for brittle THE transition from ductile to brittle fracture with decreasing temperature remains of extreme interest especially among the refractory metals, such as tungsten, molybdenum, and chromium, which have relatively high transition temperatures. Fracture, yield stress, and hardness. Tension tests at a strain rate of 0.015 per min were generally utilized. Results are interpreted in terms of the quantity of each element retained in solid solution. Of these elements, chromium has been studied the least, but deserves additional attention because of its superior oxidation resistance for high-temperature use. In the past, impurity elements which have received attention are carbon, nitrogen, oxygen, and sulfur;'-' of these, nitrogen has usually been considered to be the most detrimental. Unfortunately, because of different levels of both specific and total impurity content, and because of the many different test and evaluation techniques used, a clear, definitive picture of brittle fracture in chromium has not been forthcoming. However, many

Jan 1, 1964

By M. Bevis, A. G. Crocker

A. G. Crocker and M. Bevis (Battersea College of Technology)— Richman and Richman and conard17 have recently published the very interesting results of their studies on the plastic deformation of Fe-Ni-C martensites and of an Fe-5 wt pct Be alloy. Other work on the range of Fe-Be alloys containing between 16 and 27 at. pct Be has also been reported by Richman." One of the fascinating features of this work is that the materials investigated deform primarily by means of twinning and that several twinning modes are operative in addition to the well-established (112 ) mode of bcc materials The composition planes of these unusual twins were determined using a single-surface analysis and reported as (0131, "{045)" or "{089)", and It is now thought1' that the "{0,1,13)" habit reported for the Fe-Ni-C alloys'' is more likely to be near "{127)". Although the full twinning elements of these unusual twinning modes could not be determined directly from the experimental results, the authors attempt to deduce the elements by considering twin intersectionslQ and by using the projection technique of Jaswon and Dove. The basic assumption of their approach is that the (013) habits are truly rational planes but that the other habits are irrational and merely approximated to by the indices quoted above. They thus deduce that the twinning mode describing the (013) habit is either Type I or compound and that the modes describing the other habits are Type 11. This deduction must however be false as all twinning modes in cubic structures obeying the classical orientation relationships of deformation twinning must be compound. Type-I and Type-I1 modes can occur in all of the other crystal systems (indeed in the triclinic system compound modes are not allowed), but in the cubic system only compound modes can arise. This fact, which does not appear to be well-known, fol- lows immediately from the relations between the four twinning elements defining a twinning mode. Thus for a Type-I mode which is uniquely defined by the rational twinning elements K1 = hi and given by: where the summation convention of the tensor calculus has been adopted. For cubic materials the metrics and reduce to the unit tensors and j so that we have It is clear from these equations that both ki and ui must take on integral values; i.e., Kz, and ql must be rational, if hi and vi are integers, i.e., if K1 and are rational. Thus for cubic materials a Type-I mode must degenerate into a compound mode and the same result also arises for Type-II modes. The apparently irrational habits observed by the authors can thus not be explained in terms of Type-I1 twinning if the classical laws of deformation twinning are to be obeyed. An alternative explanation of the irrational habits is that they may arise from twinning modes with four irrational twinning elements. These modes, which do not obey the classical orientation relationships associated with deformation twinning, have been shown to arise as the result of double twinning processes in magnesium,22 but may also describe a simple shear on an irrational plane in an irrational direction. Indeed double twinning processes in bcc

Jan 1, 1963

By S. J. Rothman, L. T. Lloyd

S. J. Rothman and L. T. Lloyd (Argonne National Laboratory)— Hagel's paperz0 discusses the question of the mechanism for self-diffusion in bcc transition metals. Recent work21"23 has led us to agree with him in reabandoning the ring mechanism in favor of a defect mechanism, most likely vacancies. On the other hand, we think that Hagel's attempt to group together all self-diffusion in bcc transition metals is wrong. We prefer the scheme of Peart, Graham, and omlin," who separate them into two groups. One group contains the anomalously behaved metals P titanium,', y uranium, and perhaps zirconim.' The other group contains a iron," this alloy was held at 1800°C for 2 hr before quenching, its structure was all a. B. C. Giessen, I. Rump, and N. J. Grant (Authors' reply)—We very much appreciate the discussion by Deardorff and Kato regarding the a to /3 transformation temperature of hafnium. In the W-Hf program, as well as in a current study of the system Cr-Hf, standard precautions were exercised against contamination, including vacua of less than 10"5 mm Hg and a weight control check of all specimens to insure an impurity rise of less than 100 ppm. Following receipt of the above discussion, a revision was made in the annealing process. Arc-cast specimens were etched with a 10 pct HF-90 pct HNO solution until 1 mm of surface, including a possible oxide film, was removed. Annealing was done in a hafnium container which provided a long diffusion path for gaseous contaminants. Finally, the heat treating time was shortened. Structural changes were noted to occur quite slowly. A 99.5 at. pct Hf alloy showed 70 pct /3 after 30 min at 1700°C and was 100 pct /3 after 10 min at 1715°C. After 24 hr at 1740C, the alloy was found to be 10 pct/3. This change is due to contamination; it was estimated that it corresponds to an increase of 60°C in the transformation temperature over a 24 hr period. The corresponding change in 30 rnin would be slight. Using the same hafnium as in the above publication, and three new alloys at 98, 99, and 99.5 at. pct Hf, the transformation temperature was indicated to be 1715" 15°C. Since this hafnium contained 4.4 at. pct Zr, a correction of 40 5C, based on an assumed approximately linear transformation temperature curve, must be made for pure hafnium. This yields a value of 1755 20°C in good agreement with Deardorff and Kato's value. Because the slope of the boundary is small, this permits a good extrapolation, and we regard the W-Hf alloys as well suited to check the Hf transformation temperature. niobirn,'' and molybdenum,22 whose activation energies correlate with the melting temperature and whose Do values follow Zener's predictions.28 We have no quarrel with Hagel's placing chromium into the second group; we disagree with his interpreting our data to make uranium fit into that group. Hagel considers that the measurements of self-diffusion in uranium below about 950°C represent combined volume and grain boundary diffusion. This contention is based on the curvature of the penetration plot for our 891°C run,4 which also has a nearly straight line plot of log c vs x. Hagel has extrapolated these characteristics to our 803.5C run and fitted his Arrhenius plot for self-diffusion in y uranium to our four highest temperature points only. We think this is wrong for the following reasons.

Jan 1, 1963