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By Rodney P. Smith

The diffusivity of carbon (0.1 wt pct C) in Fe-Nz alloys (0 to 100 pct Ni) has been determined for the temperature range 860° to 1100°C. As a function of nickel content, the diffusivity has a maximum near 60 pct Ni (the maximum diffusivity being about 1.3 times that in the absence of nickel); the activation energy has a maximum between 40 and 50 pct Ni and a maximum between 80 and 90 pct Ni. The difference between the minimum activation energy and that in iron is about 3000 cal pev g-atom; Do has a minimum between 40 and 50 pct Ni and a maximum between 80 and 90 pct Ni. The results cannot be rationalized by an approximate thermodynamic treatment. THE diffusivity of carbon has been determined in a number of iron alloys over a limited concentration range. It seemed desirable to investigate a system which allows an extended range of alloy composition within a single-phase region. The Fe-Ni system is ideal in this respect, in that all alloys from 100 pct Fe to 100 pct Ni are fee in a convenient temperature range.&apos; The carbon diffusivity was determined by a decar-burization method. The experimental procedure was identical with that used to determine the diffusivity of carbon in y Fe-Co alloys.2 The experimental data are given in Table I. A small correction (order of a few percent) has been made to the measured carbon loss to correct for the carbon lost from the ends of the cylinders.&apos; Since the diffusivity of carbon varies with carbon content the measured diffusivity is an average value for a carbon content between zero (surface) and that at the center of the sample at the end of the decarburization periods. In making the correction in D to 0.1 wt pct C it is assumed that the measured D corresponds to the arithmetical mean of the carbon content at the surface and at the center of the sample at the end of the decarburization period.3 Since this correction is small (<4 pct in D) and since for our decarburization times the changes in carbon content at the center of the sample was small the mean carbon content could have been taken as half the initial value. It is further assumed that the change in D with carbon content for the alloys is the same as that for the diffusion of carbon in iron. From the data of Wells, Batz, and Mehl4 and of smith5 the correction of D from the mean carbon content to 0.1 wt pct C is 0.3 (0.1 - mean wt pct C). The results for iron are given in Ref. 2. Within the experimental error log Do.l%C for each alloy is a linear function of 1/T; the constants for the equation determined by the method of least squares are given in Table I. The deviations of the experimental points from the least-squares line are of the order of 2 pct in D. A comparison of our results for the diffusivity of carbon in nickel with those of other investigations is shown in Fig. 1. The lower curve in Fig. 1 is a linear extrapolation of values calculated* from the equation of Diamond6 for the relaxation time (temperature range 100° to 500°C). The results indicate a small increase in the activation energy over the temperature range 100° to 1400°C; however, it is difficult to say whether the change in Q is real or experimental error. Certainly the change in Q is less than the variation of 5 kcal per g-atom in the diffusivity of carbon in a iron.6 The experimental data for all the alloys are plotted in Fig. 2. As a function of nickel content the diffusivity has a maximum near 60 wt pct Ni at all temperatures investigated and possibly a minimum between 80 and 90 wt pct Ni for temperatures below 1000°C. The activation energy, Q, and log Do are plotted as a function of the nickel content in Fig. 3. Due to the limited temperature range of our experiments neither Q nor Do can be determined precisely; the activation energies appear to be consistent to ±0.3 kcal per g-atom; however the deviation from the absolute values may be considerably larger, see Table II. The Do values probably have little significance. The solid line for Do in Fig. 3 represents the values required to reproduce the experimental values for D when Q has values represented by the upper solid line The diffusivity of carbon may be expressed in terms of the mobility B22, the activity coefficient r2,

Jan 1, 1967

By J. H. Swisher

When an Fe-Mn alloy is internally oxidized, the inclusions formed are MnO which contains some dissolzled FeO. In the internal oxidation reaction, not all of the manganese is oxidized; some remains in solid solution as a result of the high Mn-0 solubility product in iron. Taking these factors into consideration, the rate of internal oxidation of an Fe-1.0 pct Mn alloy is computed as a function of temperature, using available thermodynanzic data and recently published data for the solubility and diffusivity of oxygen in iron. The predicted and experimentally determined rates for the temperature range from 950 to 1350°C are in good agreement. ThE rates of internal oxidation of austenitic Fe-A1 and Fe-Si alloys have been studied extensively.1"4 Schenck et al. report the results of a few experiments with Fe-Mn alloys at 854" and 956C, and Bradford5 has studied the rate of internal oxidation of commercial alloys containing manganese in the temperature range from 677" to 899°C. When Fe-Mn alloys are internally oxidized, the inclusions formed are solutions of FeO in MnO, the composition depending on the experimental conditions. Since the thermodynamics of the Fe-Mn and FeO-MnO systems have been investigated,6"9 and since the solubility and diffusion coefficient of oxygen in y iron have been determined recently,&apos; it is possible to predict the rate of internal oxidation from known data. The calculations used in predicting the rate of internal oxidation will first be outlined, then the results of the prediction will be compared with the experimental results of this investigation. PREDICTION OF PERMEABILITY FROM THERMODYNAMIC AND DIFFUSIVITY DATA Oxygen is provided for internal oxidation in these experiments by the dissociation of water vapor on the surface of the alloy. The dissociation reaction is: + H2(g) + [O] [1] where [0] denotes oxygen in solution. The equilibrium constant for this reaction is known as a function of temperature:&apos; log As oxygen diffuses into the alloy, oxide inclusions are formed which are MnO with some FeO in solid solution. The reactions occurring are: [Mn] + [0] = (MnO) [31 and [Fe] + [0] = (FeO) [41 where [ Mn] is manganese dissolved in iron and (FeO) is iron oxide dissolved in MnO. The overall reactions may be written as follows: [Mn] + HOte) = (MnO) + H2(£) [5] and [Fe] + H20(g) = (FeO) + Hz(R) [61 The standard free-energy changes and equilibrium constants for Reactions [5] and [6] are known.6 Therefore the equilibrium constants for Reactions [3] and [4] may be obtained by combining known thermodynamic data for Reactions [I], [5], and [6]. For Reactions [3] and [4]: K = and For the present purpose, both the Fe-Mn7,8 and FeO-~n0&apos; systems can be considered to be ideal, i.e., [amn] = [NM~] and (aFeO) = (NM~~) = 1 - (NFeO) where the Ns are mole fractions. These relations, together with Eqs. [I] and [8], permit us to compute both the oxide and metal compositions as a function of temperature and oxygen potential at any point in the specimen. For cases where the oxygen concentration gradient between the surface and the subscale-base metal interface is linear, the kinetics of internal oxidation is an application of Fick&apos;s first law: where dn/dt is the instantaneous flux of oxygen into the specimen, g-atom per sq cm sec; 6 is the instantaneous thickness of the subscale, cm; Do is the diffusion coefficient of oxygen in iron, sq cm per sec; p is density of iron, g per cu cm; h[%O] is the oxygen concentration difference between the surface and sub-scale-base metal interface, wt pct. B6hm and ~ahlweit" derived an exact solution to the diffusion equation for systems in which there is a stoichiometric oxide formed. They showed that the oxygen concentration gradient is given by a rather complex error function relation. For the Fe-Mn-0 system and for most other systems that have been studied, however, variations in oxide compositions are small and rates of internal oxidation are sufficiently slow that the deviation from linearity in the concentration gradient of oxygen is negligible. The mass of oxygen transported across a unit area of the specimen for the total time of the experiment is given by the mass balance equation:

Jan 1, 1969

By HILLARY W.

THAT colleges and technical schools constitute a vital factor in our industrial system is being realized more and more of late years. Consequently it is desirable that there should be a constant interchange of ideas between the &apos;school and the industries and that there should be a more intimate contact between the student and his future employer. Business and industry demand certain proficiencies and qualifications of the student and he, in turn, sees certain rewards and advantages in the industry. . In a meeting of this kind, whose primary purpose is to promote a greater intimacy between the students and those men who are active in the mining profession, it is quite fitting that each state his demnds upon the other in order to establish a common understanding. It is probable that a student, not being conversant with actual conditions in the industry, may be unfair in what he asks of his employer. Therefore criticism, constructive or other- wise, is not only accepted, but is invited.

Jan 1, 1930

By Joseph Taylor

THE Ducktown district is in the extreme southeastern corner of Tennessee, its principal railroad point being Copperhill, on the Blue Ridge division of the Louisville &Nashville Railroad, midway between Knoxville, Tenn., and Atlanta, Ga. The ore deposits were discovered about 1849 and development work was begun in the early fifties. Only the "black copper? ores, products of secondary enrichment, from beneath the gossan outcrops and overlying the massive sulphide deposits, were then mined and smelted for their copper content. Upon their exhaustion, attention was directed to the treatment of the pyritic ore remaining, resulting in the devising of a, process consisting of open-heap roasting, followed by blast-furnace smelting, which was practised until 1903, when semi-pyritic smelting was-adopted. In 1908, the companies operating in the district; on account of litigation brought about by alleged smoke damage to forests and vegetation in the adjoining counties of Georgia, were compelled to erect enormous acid plants to prevent the escape of the sulphur dioxide produced in the smelting operations. The utilization of this sulphur dioxide in the, manufacture of sulphuric acid as a byproduct has added to the revenues of the companies, and at the same time has furnished a valuable source of supply of sulphuric acid to the fertilizer trade of the South, and more recently to the manufacturers of explosives for use in the production of war munitions. The steadily increasing demand for sulphuric acid for the manufacture of fertilizers and explosives, together with the decreasing imports of pyrites, from which the acid is generally produced, now makes it imperative that greatly extended resources of pyrite be developed. While the Ducktown deposits do not predominate in pyrite, they do contain an inexhaustible supply of pyrrhotite, admixed with pyrite, which can be satisfactorily employed to supplement or substitute for pyrite in acid making.

Jan 2, 1918

By R. H. Lee

Without doubt, one of the most frequent and serious ani~oyailces connected with the practical running of a blast-furnace, especially in single-furnace plants, is caused by low steam, in spite of the fact that all boilers at blast-furnaces have grates for burning coal, and that coal is more or less continuously burned upon them, from three to a dozen men being pretty constantly engaged around the boilers as firemen or coal- and ash-handlers. At times, when the furnace is " tight," all available men arc put on to assist the regular firemen; yet sufficient steam cannot be got to keep the engines up to their regular number of revolutions, while the stoves, deprived of the gas which has been sent to the boilers, run cold, so that, when the furnace loosens up and resumes the regular rate of driving, the blast is very considerably below normal temperature, and a "cold," or at best a " high-sulphnr," cast is the result. Again, it often happens that a furnace, running at its best, becomes temporarily a little too hot: the pressure rises; the amount of gas made is diminished; the steam soon commences to go down; and a small scaffold is likely to form before the furnace has been brought back to the proper rate of driving, and thus enabled to take its regular amount of blast. The usual remedy is either to "jerk" the furnace by a sudden, brief intermission in blowing, or to cool the furnace by lowering the heat of the blast; but if the lower blast-temperature be maintained too long, the hearth and descending stock may be cooled below the " critical temperature" mentioned by Mr. Johnson,&apos; and the furnace may go to the other extreme, and become cold. This is especially the case when coal or coke high in sulphur is used.

Jan 1, 1907

By B. H. Caudle, L. G. Davies, I. H. Silberberg

This paper presents a method of predicting the recovery and performance of a five-spot steam injection project, in which a realistic approach to pattern sweepout efficiencies is made. Published methods for radial systems were modified for the five-spot pattern by approximating the stream lines with straight lines radiating from the injection well and then converging to the producing well. In each radial segment, the position of the steam front and the temperature profile ahead of the steam front were determined by heat balance equations, which included an estimation of heat losses to surrounding formations. The location of the saturations behind the cold water front was determined from a Buckley-Leverett solution to the material balance equation. Results from this program show steamflood recovery in a five-spot pattern to be considerably less than that predicted for true linear or radial flow systems. For a specific reservoir containing 900-cp oil, a steamflood in a purely radial flow system was predicted to recover more than 75 percent of the original oil in place when 2 PV of water had been injected as steam. A five-spot steamflood with otherwise identical properties was predicted to recover 10 percent of the original oil in place when 0.15 PV of water had been injected as steam and to recover almost no oil thereafter. A cold water five-spot flood in this system was predicted to recover approximately W percent of the oil in place with I PV of water injected. For a five-spot pattern in an example reservoir with 10-cp oil, steam injection similarly showed lower ultimate recovery than water injection but no improvement in recovery rule. Introduction The thermal recovery method considered in this study is steam injection in a five-spot pattern. Pattern steam injection has been given little attention in the past, possibly because of some rather obvious disadvantages. Unless steam temperature is maintained throughout the entire swept area, the process will revert to simple waterflood with all heat being lost prior to reaching the oil bank. Also, the oil viscosity reduction takes place near the steam front and not around the producing wellbore, so that low producing rates must still be endured. This is the reason for the success of the steam stimulation, or cyclic injection, in which the fluids are produced from the same well used for injection. On the other hand, steamflooding can offer some advantages. Oil displacement is by four methods: (1) mechanical displacement by the condensed water, (2) viscosity reduction of the crude oil, (3) swelling of the crude oil, and (4) distillation of the crude oil in the steam zone. Although dependent upon the crude, laboratory experiments have shown displacements up to 80 percent by steamflooding. In addition, steam is a good heat transport medium, since it is cheap and has a high heat content. Previous Investigations Previous publications have reported methods for predicting recovery in a steamflood for linear and radial systems. Since no pattern sweep efficiency is taken into consideration, the recovery even from a radial system must be greater than from more realistic geometries such as the very common five-spot patterns. Probably the broadest coverage is given by Willman who reported experimental results and offered a method of predicting recovery for a radial flow system. They concluded that both hot water and steam injection recover more oil than an ordinary waterflood, and that steam injection could yield recoveries "as much as 100 percent greater than by water flood." They also concluded that both the heat requirements for a reservoir and the residual oil remaining in the reservoir after steam injection were independent of the amount of oil originally in place, that short exploitation times were desirable, and that a high percentage of net sand in the reservoir with a high initial oil saturation was desirable. The method assumes that the flood occurs in three concentric cylindrical zones: (1) an inner steam zone, (2) a central hot water zone, and (3) an outer cold waterflood zone. Displacement in the steam zone is based on laboratory-determined residual oil saturations while the hot water and cold water zones use the conventional Buckley-Leverett equations. Although the results shown by Willman et al. are for a radial system flowing out from the well to an assumed external circular boundary, their equations did

Jan 1, 1969

By S. F. Radtke, J. A. Snyder, R. M. Scriver

DISCUSSION, J. R. Long presiding R. I. Jaffee (Battelle Memorial Institute, Columbus, Ohio)—The authors have written a fine and important paper, and are to be congratulated. I do not entirely follow their discussion of the relationship between the ductility of titanium and its crystal structure. Since high purity titanium is extremely ductile, being capable of cold reductions of ovei- 99 pct, its ductility cannot be unduly restricted by its hexagonal crystal structure. It is true that interstitial solid solutions of nitrogen and oxygen do have a restricting effect on ductility, but this would appear to be an alloying effect rather than a crystal structure effect. The point made by the authors concerning the relative ductility between forged and rolled titanium does not appear to be conclusive, either. It would appear that in the same condition forged material would have equivalent or better ductility than sheet material. The difference between the ductility reported for forged bar and annealed sheet in Table I may be the result of a greater degree of cold work in the as-forged condition. S. F. Radtke, R. M. Scriver, and J. A. Snyder (authors&apos; reply)—We appreciate the discussion by Dr. Jaffee. His point is well taken that the hexagonal structure of titanium does not, in itself, restrict the ductility of iodide material and, therefore, should not be limiting in this case. It is true, however, that the ductility of different grades of titanium is not necessarily related to their hexagonal structure but more likely to their orientation and composition. It is also true that the presence of small amounts of foreign elements in hexagonal metals may have more pronounced influence on ductility than a corresponding quantity in cubic metals. Average values from a large number of tests might show relatively better ductility for forged titanium than is recorded in Table I. The forged bars used in this work were tested in the annealed condition; little is known concerning the effect of forging practice on ductility in titanium metal.

Jan 1, 1952

By C. E. Wood

THE Blast Furnace Studies Section, Metallurgical Division, Bureau of Mines, has been working for several years on the mechanism of desulphurization of iron and steel by slags. The usual assumption that desulphurization takes place by diffusion of FeS from metal into slag and subsequent reaction of this FeS with CaO to produce CaS has seemed to us inconsistent with a number of experimental results we have obtained. We undertook, for example, to determine the proportion of sulphur in a slag present as FeS. An entirely satisfactory method of doing this has not yet been evolved. The results of extraction with metallic antimony led to an interesting conclusion, however. FeS is readily soluble in metallic antimony, either physically or by chemical reaction. On the other hand, CaS was found to be insoluble. Hence it would appear that by rapid extraction of the slag with antimony we might expect to determine the distribution of sulphur between iron and calcium. The results showed that much of the sulphur was present as FeS. In some instances the extraction of sulphur as FeS was almost quantitative. For example, in a slag containing 3.8 grams Fe and 3.7 grams S, extraction removed 1.18 grams S and 2.12 grams Fe. If all the iron present in the antimony had been FeS, 1.21 grams S would have been extracted. In another slag with 8.6 grams Fe and 0.06 gram S present, 0.14 gram Fe and 0.08 gram S were extracted. This was obviously extraction of sulphur as FeS within the analytical error and showed that FeS was present either in solution or as a dispersion. Attempts to determine the solubility of FeS and CaS in slag by quenching and ultramicroscopic investigation have indicated that the solubility of FeS is very low, and that reactions in the slag are probably not to be considered as homogeneous. A more detailed report on these theoretical considerations will be made at a later date.

Jan 1, 1939

By Maurice Cook

NORMALLY the grain size of cold-rolled and annealed copper sheet is of the order of 0.02 to 0.06 mm., and 0.1 min., for example, would, for many purposes, he regarded as undesirably large. The occurrence of very large grain sizes in a few isolated cases of copper sheet led the authors to inquire into the causes giving rise to such unusual results. During the course of this work a very large number of experiments have been carried out to determine the effect of varying the conditions of the final and penultimate rolling and annealing operations, as well as of earlier rolling and annealing treatments. A correspondingly large number of observations have been made, but within the space of one paper it is possible only to outline relatively briefly what appear to be the more important of these experiments and observations. The presentation of the results does not follow chronologically the order in which the experiments were carried out and they have been rearranged for the sake of simplicity. In recent years a considerable amount of work has been done in connection with the recrystallization and grain growth in metals and alloys that take place on annealing, and a number of generalizations have been reached. It is known that the crystal size in wrought material in the annealed condition depends on a number of factors, including the time and temperature of the annealing operations and the nature and amount of cold-work to which the material has been subjected. Results, however, that are not covered by these generalizations can be obtained, which, in some instances, may even appear to he contradictory to them. According to these generalizations gradual changes in grain size are effected by progressive variation of the factors involved in annealing or cold-working. The work recorded in the present paper, however, relates to the development of grain sizes which are far beyond those normally encountered in ordinary annealing operations and far in excess of grain sizes which, according to ordinary standards, would be classified as coarse or large.

Jan 1, 1938

By M. H. Merriss

Some years ago, at the plant of the Baltimore Copper Smelting & Rolling Co., the receipt of large quantities of copper blister running high in lead, nickel, and arsenic resulted in the formation of a great amount of very foul slag, in the anode furnaces. A typical analysis of this slag was: Gold, oz. per ton......... 0.09 Arsenic, per cent.......... 0.60 Silver, oz. per ton......&apos;.. 13.20 Antimony, per cent........ 0.50 Copper, per cent......... 19.50 Silica, per cent............ 28.30 Lead, per cent........... 11.90 FeO, per cent............. 19.20 Nickel, per cent.......... 4.60 CaO, per cent............. 1.60 The problem was to get out the copper in marketable form, to save the gold, silver, and particularly the nickel, and to get rid of as much as possible of the lead, arsenic, and other elements that were valueless to the Baltimore plant. In a copper refinery that does not take custom material for matte smelting, the usual method is to smelt the anode slag with coke in a reducing furnace, the black copper thus formed being sent back to the anode furnaces; this was the custom at Baltimore. An average anode slag will contain, perhaps, 40 per cent. copper and such small quantities of lead, nickel, etc., that smelting will get rid of most of these impurities in the black-copper furnace slag. To treat such an impure slag in this way, however, would result in a large nickel loss, and would send back to the anode furnaces all the lead and nickel not so lost, where it would be slagged off again and returned to the black-copper furnace as a slag still more concentrated in impurities. The result would probably be a constantly increasing amount of anode slag containing a likewise constantly increasing percentage of impurities. To avoid such a disastrous closed circuit some other process had to be devised. A small multiple-tank room, built for impure copper as an adjunct to the main series electrolytic refinery, was available, so the following standard process was suggested:

Jan 1, 1924

By Charles O. Burgess

The improvement in the quality of cast iron by means of alloy additions has been a metallurgical accomplishment of recent years. Work in this field has shown that chromium is one of the most effective of such additions but, in general, the influence of chromium has been studied only in connection with other alloying additions, with irons other than foundry irons, or with relatively high percentages of chromium. The present study was initiated for the purpose of determining the influence of small additions of chromium (0.25 to 1.00 per cent) on the quality and resultant properties of cast irons of various foundry grades. The effect of small chromium additions on cast iron was investigated with particular reference to casting characteristics, hardness vs. section, strength, machinability, heat resistance and structure. Material Tested Three separate types of cast iron were investigated as to the effect of small chromium additions. The first series of these irons was prepared from remelted foundry cast iron at the Union Carbide and Carbon Research Laboratories, and the other two series consisted of cupola melts made under usual operating conditions. The first series was made by melting 30-lb. charges of foundry scrap iron containing 2.86 per cent carbon, 2.72 silicon, 0.50 manganese, 0.062 sulfur and 0.794 phosphorus in a carbon resistance furnace. The chromium was added as high-carbon ferrochrome just before pouring. The irons were cast at approximately 1250" C. (2282" F.). The analysis and physical properties of these irons are given in Table 1, test 1. The second set of cast irons was made in a cupola in accordance with normal practice, the charge containing approximately 42 per cent steel scrap and the chromium additions being made to the ladle. Analysis and tests of these heats are shown in Table 1, test 2. A small amount of copper was present in heat C of this series. Further data on the effect of chromium on strength were obtained from a third series of 13 cupola heats containing from 0.06 to 0.50 per cent chromium and made without steel additions. The heats were all

Jan 1, 1933

By W. W. Gorr, R. Smith, E. H. Wyche

THE combination of high strength and corrosion resistance of cold-worked 18 Cr, 8 Ni steel has been advantageously utilized for some time, particularly in aircraft and rail car structures. There are, however, certain limitations on the use of such materials because the high strengths can be obtained only by cold-working, limiting the available products to sheets, strip, wire and tubes. The authors sought to overcome these limitations by resorting to precipitation-hardening, which has been used so successfully in nonferrous metallurgy but only to a limited extent in iron-base alloys. Accomplishment of this objective not only overcame the limitations, but also effected certain improvements in mechanical and other properties. This paper is an account of the development by Carnegie-Illinois Steel Corporation of a precipitation-hardening 18-8 stainless steel (called Stainless W? and tentatively identified as type 322). A description is given of its composition and metallurgical characteristics, heat-treatment, physical and mechanical properties and corrosion resistance. DEVELOPMENT OF THE NEW STEEL For a considerable length of time the authors were unable to determine the mechanism of the precipitation-hardening process that had been noted by Ffield 18,19 in 18-8 Ti or 18-8 Cb after cold-working and reheating to moderately elevated temperatures. All known variables were exhaustively studied, but with little success. However, results began to indicate that chemical composition was the most important variable, particularly the ratio of austenite-forming to ferrite-forming elements. The investigators &apos;then focused their attention upon the composition, and, in particular, upon the element titanium and its mode of alloying in the presence of other elements. A heat was obtained that could not be brought to the softness level of annealed 18-8. The response to cold-straining and aging* was very marked by previous standards, and, more important, cold-straining was found to be entirely unnecessary to produce the precipitation-hardening effect. The chemical composition of this heat was: C, 0.06 per cent; Mn, 0.54; P, 0.016; S, 0.016; Si, o.58; Ni, 7.28; Cr, 17.6o; Ti, 0.90; Al, 0.17. For some time the development work, particularly on composition, was carried

Jan 1, 1946

By C. Hays, R. E. Swift, E. G. Kendall

Investigations of the Zr-Pt system, by metallography, incipient melting, and X-ray diffraction, determined the phase relationshifis from 0 to 50 at. pct Pt. Phase fields in the Pt-~ich region were outlined, and three intermetallics (ZrPt, Zr2Pt, and ZrPtd were located. A eutectic between Zr and Zr2Pt, and a eutectoid veaction between Zr and a Zr + Zr2Pt, were established. The maximum solubility of Pt in P Zr was approximately 13.5 wt pct, as opposed to less than 1 wt pct solubility in a Zr. EARLIER work on the Zr-Pt system was limited to an X-ray study on the intermetallic compound, ZrPt3, by H. J. Wallbaum,1 It was reported that ZrPt3 existed at 86.52 wt pct Pt, and had a hexagonal structure, isomorphous with TiNi3. Wallbaum&apos;s data revealed the following structural particulars: a = 5.633A, c = 9.21A, and c/a = 1.635A. Other studies allied to Zr-Pt alloys concerned only 1) Pt-rich alloys (0.05 to 5.0 pct Zr) for corrosion resistance,2 2) a Zr-base alloy with 5 pct Pt and 0.124 pct C for oxidation resistance,3 and 3) electroclad-ding of Zr with Pt for in-pile corrosion resistance of Zr to uranyl sulphate. 4 Metallographic, incipient melting, and X-ray diffraction techniques were applied to accurately resolve the phase relationships in the 0 to 50 at. pct (68.2 wt pct) Pt region, and to outline the phase fields in the Pt-rich area. Three intermediate phases: Zr2Pt, ZrPt, and ZrPt3, were also established by the same methods. PROCEDURE Melting stock for this program was of the highest purity obtainable. The Zr was iodide crystal bar with a low hafnium content of about 0.05 wt pct (Westinghouse "Grade 3"). The as-received Zr was treated to remove the surface film of corrosion product that resulted from a standard autoclave grade designation test. Next, the bars were processed to yield material suitable for arc melting and free of contaminants. Sheet platinum metal (Baker and Co. "Grade 2") was used for alloying additions. This material con-

Jan 1, 1962

By Robert F. Mehl

THIS essay is an attempt to present the elementary facts and ideas concerning the growth of crystals, especially of metals. Freezing, like all heterogeneous processes, is a process of nucleation and growth; it manifests itself in metallurgy primarily in the freezing of ingots. The preceding paper in this volume discusses nucleation; the paper to follow describes ingot solidification. The present paper will treat of the growth of nuclei to large crystals, embracing a long series of phenomena, many of which are familiar to metallurgists.† Crystal growth, it will be immediately noted, occurs not only in the freezing of metals, but in the freezing of all substances; and it is a prominent and familiar phenomenon in crystallization from solutions, aqueous or otherwise, and in crystallization from the vapor phase. It will be necessary to include such systems in this discussion, for so much of value to metallurgists has been learned from their study. Apart from this, so far as metals are concerned, it will be simpler to limit the discussion to the freezing of pure metals and of solid solutions. Other types of freezing-eutectic, peritectic, etc.-will be excluded, though they have much of interest and of importance. BASIC MECHANISM OF FREEZING Ideally, nucleation and growth processes can best be considered from the point of view of isothermal reaction and upon the assumption of random nucleation. In. such an ideal case, nuclei form at random, and at a characteristic rate either constant or changing with time, and grow to spherulites at a characteristic rate, constant or changing with time, Fig. I.. On the simplest assumption, the reaction rate-in this case the rate of freezing-is a resultant of these two component rates. The reaction rate equation may be written in terms of these two component rates. The formation of pearlite from austenite closely approaches this ideal case. The ideal case forms a very useful point of departure in considering real cases. Various factors of reality produce deviations from this assumed ideality. In freezing, the isotropic medium, the melt, passes to the anisotropic solid, the crystal. Crystals are lattices of atoms, and the unit cell is often referred to as a crystal unit. Rosenhain, many years ago, represented the nucleation and growth process on freezing in the manner shown in Fig. 2, feeling, intuitively, that there must be some crystal unit in crystal growth. It now appears that this may be true, though his picture requires much elaboration. The greatest deviation from ideality lies in the nonisothermal nature of the freezing process in metals. To approach this properly it should be recalled that many nonmetallic substances freeze slowly. Tammann, to whom we owe the classic approach, studied complex organic materials in which (as in the case of eutectoid steels at high

Jan 1, 1951

By WILLIAM J. LINNEY

MAGNETITE ore from Lyon Mountain, so- called "Low Phos Chateaugay," has long been known to the iron and steel industry for its almost complete absence of impurities. These magnetites occur along the northern foothills of the Adirondacks in several parallel and folded stringers which are continuous for several miles, striking generally northeast-southwest and dipping usually over 45° to the northwest, or roughly toward the St. Lawrence River. Ore of minable thickness is found in shoots of various sizes as to length and breadth, but of undetermined and possible great depth.

Jan 1, 1943

By R. H. Tien

Temperature distribution as well as position of the solidified front is solved by means of "heat balance integral", for the case of freezing a slab with time-dependent surface temperature. Numerical solutions for the cases of linear variation and exponential decay for surface temperature are given. Application also includes solidification of casting. An increased interest in the heat-transfer problem involving a change of phase has been developed in recent years. Practical problems include solidification of a casting, freezing and thawing of soil, ice formation, and others. Despite the importance of the topic, a literature search reveals relatively few solutions which may be extended to practical problems. Due to mathematical complexity, which comes from the nonlinearity of governing differential equations, exact analytical solutions which have been published are limited to a few cases with simple boundary conditions. Although numerical solutions of these problems have become available after highspeed digital computers were introduced, lack of simple and general methods of programming for computation makes this approach impractical. The case of the semi-infinite slab with constant surface temperature was solved in the 19th century. In honor of Neumann, who first found an analytical solution, this kind of problem is generally referred to as the Neumann solution. As has been shown in Fig. 1, the problem to be analyzed is the freezing of a semi-infinite region (x > 0) which is initially liquid at the melting temperature with the surface (x = 0) maintained at time-dependent temperature. This analysis can be applied to the study of many casting processes where most of the heat removal is essentially unidirectional. "Heat balance integral" which has been used by Goodman1 is employed in this analysis. The concept of "heat balance integral" is to define a quantity, d(t), called the thermal layer. Beyond this thermal layer, for all practical purposes, there is no heat transfer, and the region is at the equilibrium temperature. "Heat balance integral" is obtained by integrating the conduction equation with respect to the space variable over this thermal layer d(t). Choosing some plausible temperature distribution, usually a polynomial or a finite trigonometric series in the space variable, this integral equation becomes an ordinary differential equation, with time as the independent variable, which can be solved by classical methods. The thermal layer and "heat balance integral" are equivalent, respectively, to the boundary-layer thickness and the momentum integral in hydrodynamics. A modern account of Prandtl&apos;s concept of the boundary layer and von Karman&apos;s momentum integral may be found in Ref. 2. Although the problem considered here has been limited initially to uniform melting temperature, the present method is equally applicable to the case with arbitrary temperature distribution in the liquid. STATEMENT OF THE PROBLEM The physical situation and coordinate system used in the problem to be analyzed are shown in Fig. 1. Notations used are listed in the table of nomenclature. Let us assume a semi-infinite region extending over positive x, initially at the uniform melting temperature. At the surface x = 0, a time-dependent temperature, which has a numerical value

Jan 1, 1965

By Arthur F. Taggart

The following notes represent significant excerpts from a mass of records of experimental work done in the ore-dressing laborattory at the Columbia School of Mines during the years 1926 to 1928 inclusive. Classification of Experimental Work The experiments performed may be grouped for purposes of description under the following general headings: I. Collecting agents. a. A method for quantifying collecting effect. b. Coating with undissolved collecting agents (oils). c. Action of dissolved collecting agents. II. Frothing agent&apos;s. a. A method for quantifying frothing effect. b. Relation between frothing effect and chemical composition. III. Inorganic reagents. a. Methods of studying the effects of these reagents. b. Effect on slime dispersion. c. Effect on sulfides. Summary of the Origins of Present-day Flotation Practice The first practicable, foolproof method of froth flotation was described in U. S. Patent 835120, issued in 1906 to Sulman, Picard and Ballot, and in the equivalent patents in other countries. A number of less simple methods of producing the same result had been described previously in patent publications and otherwise.&apos; The reagents specified in all of these early patents were "oils" and, in addition, some inorganic substance, usually an acid. The quantities of reagents recommended and added were enormous when compared with those used today.

Jan 1, 1930

By E. J. Fasiska, H. Wagenblast

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

Jan 1, 1968

By H. T. Sumsion, A. U. Seybolt

The results of an investigation of vanadium-rich V-O solid solutions are presented, indicating the structure and lattice parameters of two solutions, a and ß, and their approximate temperature-composition existence. The a solution is the terminal body-centered cubic one, and contains up to 3.2 atomic pct 0. The ß solution has an ordered body-centered tetragonal structure, is formed at 1270°C, and exists from about 15 to 22 atomic pct 0. From the evidence available, the various phase boundaries have no appreciable temperature dependence. Evidence has been found for a polymorphic transformation in pure vanadium at 1550°C. IN an earlier investigation&apos; dealing with the preparation of pure vanadium by calcium reduction of the oxide, it was found that small amounts of oxygen drastically reduced the ductility of the metal. Because this effect was so marked, it was decided to make a study of the solubility of oxygen in solid vanadium. This report deals principally with this solubility and the nature of the phase relationships in the vanadium-rich region, particularly at temperatures below 1300 °C. However, during the investigation enough data on the V-0 system were obtained to make it appear worthwhile to present a tentative phase diagram up to the composition VO. The only significant prior work found on this system are the contributions of Klemm and Grimm,&apos; and Mathewson et al.3 Klemm and Grimm prepared a wide range of V-O compositions by powder techniques including the compositions VO.l, VO.2, VO.3 and VO4 (9.1, 16.8, 23, and 28.6 atomic pct 0, respectively). The first three compositions were found to consist of a body-centered tetragonal solid solution, while the last also showed lines of VO (NaCl structure). They found that the parameter c, increased and the parameter a, decreased with increasing concentration of oxygen. For their composition VO.27, or about 16.8 atomic pct O, they cite the values a, = 2.948A, c, = 3.53A, and c/a = 1.2. Klemm and Grimm made no attempt to determine the solid solubility limit nor to construct a phase diagram. They did, however, give some data on the homogeneity range of VO, and they proposed a structure for the body-centered tetragonal solid solution; these points will be taken up later. Materials and Preparation of Samples The vanadium used in this investigation was prepared in the laboratory by the method previously mentioned.&apos; A typical analysis is as follows: Fe, 0.007 pct; Si, 0.02; Ca, 0.06; C, 0.224; O2, 0.044; N,, 0.0017; H2, 0.003; and V, 99.34 ±0.3 (assay). The vanadium assay is probably low by about the error given. The impurities total about 0.36 which, if subtracted from 100, gives a purity of about 99.6. At the time material was being prepared for this work no suitable technique was available for melting vanadium without appreciable contamination. The procedure adopted therefore was to cut the calcium-reduced regulii into slices which were then rolled to strip about 0.025 in. thick for oxygen diffusion. Pieces of rolled vanadium of approximately 0.025xY4xl in. and weighing about 0.3 g were suspended in a vertical fused-silica tube which was part of an ordinary gas absorption apparatus. The silica tube was heated by an electric resistance-tube furnace which could be raised around the silica tube or lowered away from it as desired. This apparatus had no novel features which require detailed description. Other than the silica tube and furnace, it consisted of a glass system evacuated by a liquid nitrogen trapped mercury diffusion pump, a mercury-operated gas burette, a McLeod and a Pirani gage, and a mercury manometer. It was also equipped with suitably located stopcocks for isolating various parts of the system; the vacuum ordinarily attained was between 10" and 10-6 mm of mercury. Oxygen generated by decomposing MnO2 was passed through anhydrous magnesium perchlo-rate before introducing it into the gas burette and thence to the absorption chamber.

Jan 1, 1954

By Arthur Notman

IN VIEW of the wide publicity given to the charges by the Couzens Committee of the United States Senate of discrimination by the Bureau of Internal Revenue in favor of the copper companies, it becomes a matter of interest to consider the basis for these charges. The point to be determined is whether they rest on a foundation of fact or are purely and simply matters of opinion. The whole question boils down to the purpose of the Tax Law as applied to mines, which is to afford the same protection to them as provided for all other taxpayers, namely: that they were to be allowed to pay back as depletion to their owners the values of their properties as they existed or were estimated to exist on May 1, 1913, free from tax. To determine these valuations it was? necessary to select from a wide range of possibilities a set of values for a number of essential factors.

Jan 1, 1925