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By Ernst F. Eurich

(Cleveland Meeting, October, 1912.) ALEXANDER PARKES patented in England in 1851-52-53 a process for desilvering lead by means of zinc, making use of the greater affinity of silver for zinc than for lead, discovered by Karsten in 1842. The efforts in England to develop it commercially were not particularly successful, nor was the attempted introduction into the United States. This last was not surprising, as it was about the beginning of our Civil War, and at that period there was very little lead-bullion produced in the united States and there was no field for the process here. There was at that time on Staten Island an establishment that pattisonized lead, probably from Rossie, N. Y., and Chester, Pa., and possibly some Spanish lead, but the production of lead-bullion in the Far West had not yet begun. In 1864, Edward Balbach, of Newark, N. J., patented in this country a process for desilvering lead by means of zinc, and in 1867 Edward Balbach, Jr., patented a " movable black-lead retort with a neck, placed in a furnace," for the purpose of distilling the alloy of zinc, lead, and the precious metals. A brief comparison of the Parkes and the Balbach processes is interesting. The Parkes process as practiced in England consisted in stirring into silver-bearing lead, melted in a kettle, from 1 to 2 per cent. of zinc, cooling, skimming the alloy of lead, zinc, and silver that rose to the surface, liquating it in an iron retort, distilling the residual rich alloy in fire-clay retorts, thus regaining the zinc, and refining the desilvered lead at a low heat in a shallow cast-iron pan that formed the hearth of a reverberatory furnace. If the lead was too impure, it was first softened * Presented also at the Joint Meeting of the Institute and Section IIIa, Metal¬lurgy and Mining, of the Eighth International Congress of Applied Chemistry, New York, September, 1919, and here published by mutual agreement.

Dec 1, 1912

By CHARLES DORRANGE

INTRODUCTION. CULM is a general term used in the anthracite regions for many years to denote a mixture of coal, bony coal and impurities which is sent to the refuse-banks. Thus, 35 years ago culm contained the pea and buckwheat sizes of anthracite; but to-day, and as mentioned in this paper, culm is used specifically to denote the material which passes through the smallest screen in the anthracite-breaker. The smallest size of commercial anthracite is known as No. 3 buckwheat, barley, or bird's-eye coal, and is ordinarily made through a round-punched plate having openings 3/16 in. in diameter, and over a round-punched plate with opening 3/32 in. or 1/16 in. in diameter. Thus culm will consist of coal, bony coal, slate, gravel, iron pyrite, etc., ranging in size from ? 3/32 in. down to dust. Other local terms for culm are " slush," " silt," and " dirt." The first experiments towards the utilization of anthracite culm by briquetting, and the first briquetting-work done in this country, were in 1872 at Port Richmond Piers, Philadelphia, Pa., by E. F., Loiseau.1 Clay was used as a binder and the finished briquette was water-proofed with shellac, etc. Excessive cost was given as the reason for discontinuing work at this plant. The Delaware k Hudson Co., in 1876, built a plant at Rondout, N. Y., which operated until 1880. Gas-tar was used as a binder, and anthracite screenings were briquetted for engine fuel. Excessive cost, poor results in firing, and the tendency of the fuel to cut the boiler-flues were given as the reasons for discontinuing the manufacture. The next plant was built by E. F. Loiseau about 1878, at Nesquehoning, Pa., near the No. 1 or Nesquehoning colliery

Sep 1, 1911

By A. D. LeClaire

This paper claims to provide a description of diffusion processes in solids which is said to be a reformulation of Fick's Laws and therefore, presumably, is supposed to be as general as those laws. In fact, it appears to provide no more than an atomic model of a rather restricted type leading even to results in conflict with experiment. The restriction lies in the assumption, carried throughout the paper, that even in a chemical gradient the jump frequency i of an atom of species i is a function only of the composition on the plane from which it jumps, i.e., ?i = ?i(cl, c2 ...). This means that atom jumps in opposite directions from a site would occur with equal probability. There would then be no tendency for atoms to migrate preferentially in one direction along the gradient, so the model is incapable of accommodating the well established phenomenon of atom drift in a chemical gradient.10-" A more general model that does not suffer this difficulty was discussed in a paper13 I wrote in 1958, and the results therein already contain as a special case those given by Dr. DeHoff. The simplest sufficiently general assumption is to suppose that ?i is a function ?i(a1 a2,...; wl, w2, ..-) of the concentration aj and ? ?j at the site from which and to which, respectively, a jump is made. Any such function can always be expressed as a function of the sum and difference of its arguments. Thus d is the jump distance and g a geometrical constant. Obviously this is zero, i.e., no drift, if ??ri/??j = 0. X is written in this form, revealing two components of the total drift, because it can be shown that only the second component, depending on ??'i/???(?j -aj), actually contributes to the net diffusion flux Ji. This component can be shown,13 by a straightforward ther-modynamic transcription, to be responsible for the so called "thermodynamic factor" in the Darken approximation for a chemical diffusion coefficient is the activity coefficient of i. Because the jump rate ?i in DeHoff's approximation has no dependence on the concentration gradient it does not seem possible to derive the Darken equation from his Eq. [6] without the further rather arbitrary assumption that ?i = const ri. It is to be noted too that the author's derivation of Eq. [12] is only valid when ?i is in fact a function only of the cj at the plane from which the atom jumps—for only then is ci?i a unique function of position and therefore of A. Author's Reply R. T. DeHoff I am indebted to Dr. LeClaire for his penetrating discussion of my paper, "A Reformulation of Fick's First Law". I concede that it does appear initially that the relationship presented in my paper could be derived from the detail atomic model of random walk and atom drift presented in Dr. LeClaire's approach. However, there are some important differences in concept and viewpoint which deserve further amplification. Dr. LeClaire's description is penetrating, detailed, and fundamental. His approach describes an extremely complex phenomenon, the displacement of atoms in a multicomponent gradient, at a sophisticated level. For precisely these reasons, his analysis has not proved to be useful for experimental studies that have practical objectives. For example, in order to obtain the information required to complete the analysis of the jump frequency distribution in a ternary system, the following series of experiments would, I believe, be required: 1) chemical (gradient) experiments, covering the composition range;

Jan 1, 1970

By Raymond Ward

IN the past few years several papers have appeared dealing with different aspects of the oxidation of dilute alloys, especially with respect to the formation of internal oxides or subscales. Subscale has been defined1 as that layer or zone of oxide particles precipitated in a matrix of metallic metal in which the oxide particles are dispersed uniformly and occur by diffusion of the oxygen inward from the metal surface. Alloys composed of a solvent metal more noble than the alloying elements are subject to subscaling or internal oxidation. In these alloys the solute must be present in such quantities that if the alloy is exposed to an oxidizing atmosphere at elevated temperatures, the rate of diffusion of the oxygen into the metal will be greater than the rate of diffusion of the solute outward. There is a composition range of the iron-silicon system that falls into this classification. Knowledge of the nature and rates of oxidation of iron-silicon alloys is of great commercial importance, but very little information of this nature is available. Darken2 recently has made calculations to show the limits of concentration of silicon for which subscales are produced in iron-silicon alloys; however, the main thesis of his paper was to analyze and to explain the already existing data. The purpose of this paper is to present the effect of com position, temperature, time, and atmosphere on the type of scale-metal layer obtained and to give some qualitative indication of the effect of these variables on the rates of oxidation. Since this paper is a study of silicon steels that are available commercially, extremely low-silicon and high-silicon alloys are not included. EXPERIMENTAL PROCEDURE The alloys used in the experiment were taken from heats of silicon steel that ranged in analysis from 0.70 to 5.8 per cent silicon. This composition range takes in most of the commercial silicon steels. In Table I are listed the compositions of alloys used. Other than iron and silicon, the alloys normally contained approximately the following impurities: carbon, 0.03 per cent; manganese, 0.07; phosphorus, 0.008; sulphur, 0.02; copper, 0.07; tin, 0.01, and from nil to a trace of chromium, nickel and copper. All of the alloys used were melted in open-hearth furnaces, except where otherwise noted, and were hot-rolled to 0.100-in. plate. Samples approximately 1/2 in. square were then cut from these materials. So that the surface conditions of the samples used for oxidation would be standardized, each sample was ground through 000 emery paper immediately before oxidation. Two different techniques were employed in carrying out the oxidizing treatments. One consisted simply of heating the samples with free access to air. In this treatment the samples were set on edge on a refrac-

Jan 1, 1945

By R. H. Thurston

THE writer became convinced, many years ago, that the generally accepted values of the coefficient of friction for lubricated surfaces were not applicable to such heavy machinery as he had been called upon, in the course of professional work, to design, to construct, and to operate. Experience frequently seemed to indicate, also, a wide departure, in such cases, from the accepted "laws of friction." In the year 1869, or earlier, he invented an apparatus to redetermine these laws and these coefficients for a wide range of temperatures, pressures and velocities. The construction of the machine was delayed, however, some time, and no experiments were made for several years, when, finally, the construction of the apparatus was commenced in the workshops of the Stevens Institute of Technology, and experiments were begun in the Mechanical Laboratory organized by the writer in connection with the Department of Engineering. These machines have now been in use about five years, and have furnished an immense amount of valuable information. Those now in use are of two styles: one designed and built by the Class of 1877, Figs. 1 and 2; the other a much larger machine, Figs. 3 and 4. The first has been already frequently described,* and a working drawing of the second has been also published.† For convenience, engravings of both are herewith reproduced. In the “'77 machine,” a journal, F, is made on the overhung extremity of a shaft carried in the two bearings, B B'. This journal is grasped by brass boxes which are carried in a pendulum, II H. They are forced against the journal by a screw which compresses a coiled spring with a pressure which is read off on the scale, N H. A weight at the lower end of the arm, at I, gives it the necessary resistance to deflection. The angle of deflection is measured on the * In Scientific American, Railroad Gazette, Jour. Frank. Inst., Johnson's Cyclopaedia, Knight's Mechanical Dictionary, etc. † Railroad Gazette, Jan. 18th, 1878, p. 25.

Jan 1, 1879

By H. H. Campbell

The following paper deals almost exclusively with the results of practice at the works of the Pennsylvania Steel Company at Steelton, Pa. From the records of the furnaces at this plant, both acid and basic, large and small, are drawn the data for the various demon strations, and on a long and intimate experience with their opera tions are founded many theories and generalizations. It may seem that universal laws should not be built upon a basis so restricted ; but in reality the condition is the strongest guarantee of validity. Each table investigates some- certain variable, and by virtue of the common origin of the factors, we have good ground for assuming the corresponding agents to be equal. The examples may or may not be instances of good practice, and may be open to criticism if regarded solely as exponents of • metallurgical success. But it must be remembered that the lists are not made up of selected specimens, nor are they chosen to show su perior results; they are gathered to investigate, by strict scientific methods, the formula? of the operation. In such work no untoward results should be eliminated, save those which bear upon their face the stamp of experimental error. If the worst members be omitted, then the best must also be omitted. Only by using every available case can an honest attempt be made to deduce a true average. It is recog nized, however, that with the most careful selection it is difficult, if not impossible, to collect data representing universal conditions. In each table the records tell of a special practice, and all conclusions drawn from them are true only within the limits between which the equations have been integrated. Not assuming the prerogative of speaking for American melters in all the opinions herein expressed, nor acting as a camera in por traying an ephemeral state of national metallurgical development,

Jan 1, 1894

By H. T. Bowman

FOR more than 80 years the Bessemer process has depended upon the ability, skill, and judgment of the blower, although as early as the 1860's it was recognized that the process would benefit by some type of instrumental control.1 However, instruments with sufficient recording speeds did not exist, so the end-point determination was always dependent upon the blower's eye. This placed an obstacle in the way of precise experimental work, because of the absence of the necessary records and reference points as reported by Work.2 The use of the photocell provided the instantaneous record of the blow that made this experimental work possible and provided more scientific control for the process as discussed by Graham3' A brief description of the progress of the blow will illustrate the recording function of the instrument. The silicon in the iron is being oxidized during the first minutes of the blow, as pointed out by Henning4 in a table showing the order of metalloid elimination. The product of this oxidation is a solid that remains in the converter, so there is virtually no flame during this part of the blow. This low flame luminosity is illustrated by the flame recording shown in Fig. I, where the silicon blow is plainly marked. The dull flame of the silicon blow gradually gives way to the brilliant carbon flame as the increasing quantities of carbon monoxide formed inside the converter burn to dioxide upon contact with the atmosphere above the vessel. When the carbon reaches some low value under 0.20 per cent, there is insufficient monoxide formed to maintain the dioxide flame, so its intensity drops. Throughout the flame drop carbon continues to burn, until at some value around 0.05 per cent an arrest occurs in the recorded drop. This point has been designated as the end point. The period of time from this end point until the vessel is turned upon its side and blowing has stopped has been called the afterblow. This afterblow is used as a measure of the degree of metal oxidation, and uniformity demands that it be controlled within narrow limits. Iron and blowing conditions are likely to change several times during a turn, necessitating corresponding changes in end-point control. It is the purpose of this paper to discuss these changes, the factors that make them necessary, and their bearing upon the quality of steel. CARBON-FEO RELATIONSHIP In the Bessemer process oxidation relationships are precise. Fig. 2 shows a graph of the carbon-FeO relationship. The familiar "bomb-test" method, described by McCutcheon and Rautio,5 was used for obtaining these and all other dissolved FeO values herein reported, all tests being taken from the converter before deoxidation unless otherwise noted. All tests of 0.10 per cent carbon and above were obtained from metal blown for duplexing. McGinley and Woodworth6 reported iron oxide values for blown metal, but their tests were obtained by a different method than were those

Jan 1, 1942

By J. E. Hanlon, S. R. Butler, R. J. Wasilewski

It is known that stoichiometric NiTi transforms to a structure of lower symmetry near room temperature. The present investigation deals primarily with the changes in the electrical and magnetic properties which occur at the transformation. The effects of composition and various heat treatments on electrical properties are also discussed. In recent investigations by Purdy and Parr,' Wang et a1.,2 Dautovich and Purdy,~ Dautovich et a1.,4 and the authors, ~,' NiTi has been observed to undergo a martensitic phase transformation from the ordered CsCl (B2) structure to one of lower symmetry. The crystal structure of the low-temperature modification is still not completely worked out. This transformation occurs near room temperature for the stoichiometric composition. The thermodynamic, elastic, crystallographic, and microstructural characteristics of this transformation for some compositions have been previously reported.'-= In the present investigation, the changes in the electrical transport properties and magnetic susceptibility of NiTi when it undergoes the martensitic phase transformation have been measured. The approximate composition range covered is 48 to 52 pct Ti.* *All compositions are given in atomic percent._____________________ EXPERIMENTAL PROCEDURES AND RESULTS 1) Sample Preparation. The NiTi alloys were prepared from iodide titanium (>99.92 pct Ti) and vacuum-premelted carbonyl nickel (>99.95 pct Ni) by repeated arc melting under gettered argon and casting in a water-cooled copper mold. After the cast buttons were hot-forged at 800" to 950°C, the oxidized surface was removed by grinding and etching. Samples were cut from the worked polycrystalline buttons. After fabrication, the samples were annealed 1 hr at 900°C and water-quenched. The composition of the alloys was assumed to be the same as in the initial feed. This assumption was supported by material balance checks on 100-g arc-melted buttons which demonstrated quantitative recovery to within k0.02 pct. The oxygen content of the alloys was '150 ppma (weight) and the carbon content was 30 to 50 ppm. 2) Electrical Resistivity and Hall Effect. The electrical resistivity was measured over the composition range 48 to 52 pct Ti for temperatures varying from 4.2"K to 900°C. The high-temperature and many of the low-temperature experiments were carried out using conventional 4-probe dc techniques.7 The Hall coefficient and ac resistivity were measured at 20 cps using the apparatus shown schematically in Fig. 1. The equipment is basically an ac potentiometer: The resistive or Hall voltage of the sample is balanced by a comparison voltage provided by a dividing network across a standard series resistance. The off-balance signal is amplified by a Tektronix 122 amplifier and detected by a Princeton Applied Research (PAR) phase-sensitive detector. The precision of the resistivity and Hall coefficient measurements is i0.1 and i3 pct, respectively. The uncertainty in the data is increased by i2 pct from the precision limits because of uncertainty in dimensions and possible end effects. The temperature dependence of the electrical resistivity and Hall effect for a stoichiometric (50.0 pct Ti) NiTi sample are illustrated in Fig. 2. Above 75"C, this sample has essentially the B2 structure, while below about 0°C it is completely in the low-tempera-

Jan 1, 1968

By William R. Patterson

ACCORDING to the phase diagram for the Mn-Ni system,' the high-temperature, fcc y-manganese solid solution is stabilized to below room temperature, in the range approximately 22 to 28 wt pct Ni. However, pearson2 cites evidence in the literature showing that for manganese contents greater than about 75 wt pct the quenched phase in Mn-Ni alloys is fct. This is in keeping with zener's3 suggestion that in manganese-rich alloys the fcc high-temperature phase undergoes a diffusionless or martensitic transformation to a fct structure upon quenching. Work by Basinski and christian4 on manganese-rich compositions in the similar alloy system Mn-Cu established that in alloys of greater than about 82 wt pct Mn the y-manganese phase underwent a fee fct martensitic transformation upon quenching to room temperature. Striking evidence for this martensitic transformation was the highly twinned or banded microstructure, an example of which is shown in Fig. 1. Similar microstructures have also been found in quenched Mn-Cr5 and Mn-Au6 alloys. In the present investigation, we attempted to obtain similar evidence of a fcc — fct martensitic transformation in manganese-rich Mn-Ni alloys. Manganese alloys in the range 10 to 30 wt pct Ni were prepared by arc-melting, under argon, at atmospheric pressure. The alloys all were 50 g in size, and negligible weight loss occurred during melting. The starting materials were electrolytic manganese and nickel, both of 99.9+ pct purity. The alloys were subsequently homogenized 48 hr at 1750°F, hot-rolled 50 pct at 1700°F, annealed 2 hr at 1700°F, and water-quenched to room temperature. All heat treatment was done in purified argon. Both X-ray and metallographic techniques were used to examine the structures of the quenched alloys. X-ray diffractometer studies were conducted on powder specimens obtained from filings rean-nealed 2 hr at 1700°F in argon and water-quenched. Identification of the intensity peaks from the diffractometer counter traces showed that below about 10 to 12 pct Ni the y phase decomposed partially upon quenching to give an a- + ?-manganese structure. In the range approximately 12 to 25 pct Ni, the structure was found to be fct ? manganese with a c/a ratio approaching 1.0 at 25 pct Ni. Beyond approximately 25 pct Ni, the structure remained fcc. These results, including lattice-parameter determinations, are given in Table I. Metallographic examination. was carried out on specimens polished and etched after quenching, and also on polished specimens reannealed and quenched. In the first case, the distinctive twinning or banding so prevalent in Mn-Cu alloys was sought, while in the second, the surface relief effect generally regarded as being truly characteristic of a martensitic transformation was sought. The microstructure of representative alloys in the range 12 to 25 pct Ni is shown in Fig. 2. The structure of the Mn-15 pct Ni

Jan 1, 1965

By Thomas W. Yardley

In many years' experience as a maker and purchaser of cast-iron coated pipe, I have never met with any standard form of specifications for such. Each water-works company, employing a hydraulic engineer, has, under his direction, prepared complete specifications for the particular conditions required; but I cannot find that any two are alike; and each foundry, in bidding for the supply of such pipe, makes the price to cover the conditions' required. I, therefore, have the honor of offering to the Institute a form of specifications for cast-iron coated water-pipe, that may be found useful to water-works companies and others requiring pipe of this kind. The conditions are all reasonable, and can be carried out by makers without additional cost, and with advantage to the purchaser. Section 1 gives the kind of pipe, with its general characteristics. Section 2 specifies that neutral pig-iron shall be used, since such iron possesses the strength required, and is uniform in its shrinkage. Section 5, requiring makers to give the brands of pig-iron used

Jan 1, 1890

By H. A. Guess

A Discussion of the Paper by Mr. H. A. Guess, read at the Atlantic City meeting, February, 1904. MR. JOSEPH P. GAZZAM, Germiston, Transvaal, So. Africa (communication to the Secretary*) :-About fourteen years ago, in southeastern Missouri, I used a method for the wet determination of lead which closely resembles the modified sulphate-chromate method described by Mr. Guess. The principal difference, however, is, that after dissolving the lead chromate in hydrochloric acid, the chromic acid is determined by means of a standard solution of ferrous sulphate. The method, which I believe is still in use in southeastern Missouri, was found to be convenient and accurate for the determination of lead in the ores and various products of the mills and furnaces in that district, but it was never used for complex ores. A number of determinations of lead in mill-tailings were made in the year 1891; a few of these results are given in Table I.

Mar 1, 1905

By Phillip Crowson

INTRODUCTION This discusses some of the economic risks and uncertainties which face any company investing in new mineral ventures. These differ mainly in degree rather than kind from other large capital intensive projects, except that economic risks are compounded with technical risks. Mines face a wide variety of physical risks, and in addition the ore reserves may not prove as ample, nor as amenable to treatment as the feasibility studies indicate. On the economic front, mineral projects are subject to risks of fluctuating prices and sales volumes, no matter where they are located, or how they are financed. Typically, they are heavy users of capital compared with their owners' internally generated funds. Long term debt of various types is still the favoured form of finance. A project's currencies and cost often differ from each other and from those of the parent company. Facing up to the various risks associated with fluctuating and uncertain revenues, interest rates and exchange rates are amongst the hardest tasks for natural resource companies. ATTITUDES TO THE MINING INDUSTRY Some have questioned whether the game itself is now worth playing. They have argued that the mining industry's mediocre rewards in the past decade have been insufficient, compared with the risks involved. They can see no prospect of dramatic improvement in the next decade. Demand is highly cyclical and tends to grow less rapidly than economic activity, as a whole. Barriers to entry are low in most mineral markets, but impediments to exit can be substantial. Exit is especially problematic in those minerals where there are large state shareholdings and/or where less developed countries are major producers. The consequence is claimed to be an endemic tendency to excess capacity, and prices barely adequate to cover marginal cash costs. Many of the petroleum companies that moved into mining with such high expectations in the late 1970s have retreated, often bearing the scars of heavy losses. Individual shareholders, taken collectively, place low valuations on their investments in mining companies. The price/earnings ratios of the major mineral producing companies are low compared with their historical averages and with those of other industries. PRICE: EARNINGS RATIOS (October 1988) [UK Industrials 12.0 RTZ 8.4 Cons Gold 12.2 US Industrials 13 - 13.4 Alcan Alcoa Amax Asarco Cyprus Minerals Freeport Copper Inco Inspiration Magma Copper Newmont Mining Nord Resources Phelps Dodge Reynolds Metal Canada TSE 300 10.6 Cominco 8.7 Falconbridge 5.3 Noranda 7.0 Rio Algom 7.2 Teck Corporation 17.] NOTE: Mining companies' p/e based on prospective 1988 earnings, from Kleinwort Benson Securities' weekly Mining World, October 1988. Until 1987, it was argued that share prices correctly reflected the companies' poor earnings potential. Subsequently, the argument has been that earnings have been unnaturally boosted by cyclically high metal prices. The stock market valuations, therefore, correctly reflect future earnings, or at least expected earnings. This seems to be a case of Heads, I win; Tails, you lose. The underlying analysis of metal markets appears

Jan 1, 1990

By HERBERT G. MOULTON

FROM prehistoric times to our own day man has struggled against extremes of climate. Human life, originating in semi-tropical or temperate areas, was unable to progress into the northern latitudes until fire was discovered and some form of clothing provided. It was found possible to maintain life even in the hottest parts of the tropics, but only at a great sacrifice of comfort and efficiency compared with the more temperate zones, or in cooler areas with the protection of clothing and artificial heat. It was no accident, but the natural result of climatic conditions, that efficiency became the greatest and civilization the most advanced in areas where the natural climate was favorable, or in cooler zones where protection against severe cold could be se-cured by relatively simple methods of conserving or producing heat.

Jan 1, 1933

By H. K. Birnbaum

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

Jan 1, 1960

By M. S. Seltzer

High temperature steady-state creep rates have been determined jor lead sulfide single crystals whose defect concentrations were fixed by equilibration under controlled sulfur pressure. The activation energy of creep, Qc , for undoped lead sulfide, is a function 01 composilion, decreasing from 2.9 to 2.2 ev as the carrier concentration increases from 9 x 1016 to 8 1018 electrons cm-3 for lead excess crystals, and increasing from 1.7 to 2.3 ev as the concentration of holes increases from 4 x 1017 to 1 x 1018 cm-3 in sulfur excess material. For five different composilions, Qc for undoped and bismuth-doped crystals has been found to be equal to Qpb + Qs, the self-diffusion activation energies for lead and sulfur in PbS. It is well-established1 that high-temperature steady-state creep of pure metals is a diffusion-controlled process, where the activation energy of creep is equal, within experimental error, to the activation energy of self-diffusion. The relationship between the activation energy for steady-state creep and those for self-diffusion in binary compounds is more complicated, however, because two different diffusing species must be considered, and becayse the activation energies may be influenced by compositional variations and by foreign atom additions.2-4 In some cases experimentally determined creep activation energies are correlated with those for self-diffusion of the slower-moving species, but such agreement is by no means universal. Interpretation of experimental results is difficult because few investigations include measurements of creep rates and self-diffusion coefficients of both diffusing species on single crystals of similar composition and foreign atom concentration. The objective of this investigation, therefore, is to determine the influence of stoichiometric defects and foreign atoms on steady-state creep and self-diffusion for a well-characterized binary compound. Lead sulfide, a compound semiconductor which crystallizes in the NaC1-type structure, and whose homogeneity range includes compositions on either side of the 1:l atom ratio, was chosen for study in this investigation. The pressure-temperature-composition relations for PbS are available,5,3 and deviations from stoichiometry may be monitored by electrical measurements.7 Single-crystal specimens are available to allow observation of effects due to bulk phenomena without interference from grain-boundary effects. These crystals have been employed to determine steady-state creep rates under compressive stress for "pure" and bismuth-doped PbS as a function of sulfur pressure and temperature as well as crystal orientation and applied stress in order to establish the relationships between defect concentrations and creep rates. EXPERIMENTAL PROCEDURES Crystal Growth. Lead sulfide crystals, prepared by the Bridgman method, are grown in evacuated quartz crucibles, filled with almost equal atomic proportions of high-purity (99.999 pct) lead and sulfur, and heated to a temperature above the melting point of PbS (about 1127°C) so that the lead and sulfur react to form molten PbS. The crucible and melt are dropped through the hot zone of the crystal-growing furnace at the rate of 1 cm per hr. The maximum melting point of PbS is slightly on the lead-rich side of the 50:50 composition; hence crystals grown from a near stoichiometric melt are usually n-type semiconductors containing excess lead atoms. Typically the lead excess concentration in solid solution with the PbS is 3 x 1018 atoms cm-3. Crystals containing either 1/20 or 1/2 mole pct Bi2S3 were prepared by addition of the foreign atoms prior to crystal synthesis. Preparation of Specimens of Controlled Stoichiom-etry. Since it is difficult to grow crystals of desired composition, the process of crystal growth and control of stoichiometry are separated into two distinct operations. Equilibration of as-grown PbS to a desired composition is most easily accomplished by first annealing the n-type crystals under high sulfur pressure (about 1 atm) at temperatures above 700°C. This process serves to put excess lead precipitates into solution, yielding 0 -type crystals upon quenching to room temperature. Inter diffusion occurs readily in crystals so treated, and the methods described by Bloem may then be employed to obtain crystals of controlled stoi-chiometry. For the creep measurements made in this study, this involves heating crystals in mixtures of H2 and H2S The equilibrium constant for H2S is given by: Thus the sulfur partial pressure is obtained from knowledge of the H2/H2S ratio and Kh2S for the temperature in question. Fig. 1 shows the p-T-x diagram for PbS. It can be seen that, within the stability limits for single-phase lead sulfide, desired compositions may be obtained by equilibrating under a specified sulfur pressure and temperature. Characterization of Crystals. The principal methods for evaluating PbS crystals include measurement of electrical properties and mass-spectrographic analysis. The measured electrical parameters include Hall coefficient, conductivity type, and electrical resistivity Bloem7 has shown that there is a 1:l relation between the defect concentration and carrier concentration obtained. Hence, if the contribution to the carrier con-

Jan 1, 1968

By C. Feng, I. R. Kramer

A study was conducted to determine the influence of the surface on the yield point of fcc metals and high-purity iron. For the high-purity fcc metals, the yield Point produced by restraining a specimen may be eliminated by removing a sufficient amount of the layer. A yield point similar to that in fcc metals was found when iron specimens were pre-strained after a prior deformation. This yield point is not due to an aging effect but is associated with the surface layer. The yield points in age-hardenable aluminum alloy and those connected with "work softening" are not affected by a surface-removal treatment and are, therefore, caused by bulk-type dislocation reactions. The yield point which appears in previously strained fcc metals has been the subject of numerous studies. Several theories have been advanced to explain this "unloading-reloading" yield point. Cottrell and stokes,&apos; from their study on the effect of temperature on plastic properties of high-purity aluminum, considered that it was the result of an avalanche "breakdown" of Lomer-Cottrell sessile dislocations. Haasen and Kelly2 extended this concept of dislocation-dislocation interaction to account for the yield point when unloading and reloading was carried out at the same temperature. On the other hand, strain aging was found to be responsible for the yield point in A1-Mg alloy by Westwood and Broom,3 and in aluminum alloys containing various amounts of alloying elements by Smallman, Williamson, and Ardley.4 In these cases, the yield point is considered to be associated with the locking of dislocations by impurity atoms. Birn-baum and filer5,6 and Takamura and muira7 reported that, when a high-purity copper specimen was prestrained, then held at a lower stress, and finally reloaded at the prestrain temperature, a larger yield point was observed. Such an increase was attributed to the locking of dislocations by point defects. In addition, Bolling8 suggested that both mechanisms, i.e., dislocation-dislocation interaction and strain aging, are responsible for the yield phenomenon, at least in a brass. Thus, there appears to be experimental evidence for both the strain aging and dislocation-dislocation interaction theories to explain the yield point in the fcc metals and alloys. In a previous article,9 one of the authors observed that, if sufficient amounts of metal were electrolti-cally removed after deformation of a high-purity aluminum single crystal, the yield point did not appear upon reloading. Continued pursuit in this area revealed that the effect of the surface on the yield-point phenomenon is not limited to one metal but affects a variety of metals of different lattice structures. Nor is the effect limited to the yield points produced by simple unloading-reloading at constant temperature; the surface exerts an important role on the yield point even when the temperature is changed at some stage during the test. It is the intent of the present article to give additional information regarding the effect of the surface on the yield-point phenomenon and to show the association between the yield point in both fcc and bcc metals and the existence of a heavy concentration of dislocation in the region near the surface of a deformed specimen.10 EXPERIMENTAL Materials. The single crystals used in this study had a nominal cross section of 0.125 by 0.125 in. and a 3-in. gage length and were prepared by a modified Bridgman technique. The initial purity for the metals was 99.997, 99.999, and 99.999 pct for aluminum, copper, and gold, respectively. Bar stock of these same materials was used in the preparation of the polycrystalline specimens of aluminum and copper. The iron specimens were machined from rods of "ferrovac", reported to have a purity of 99.98 pct. In addition, a precipitation-hardening aluminum alloy, containing 1.5 pct Cu, 2.5 pct Mg, and 5.5 pct Zn, was used. The polycrystalline specimens of iron, copper, and the aluminum alloy had a diameter of 0.17 in. and a gage length of 2 in. while the high-purity aluminum specimen had a nominal rec-

Jan 1, 1965

By Paul Berggreen

LIST OF PUBLICATIONS In the Bibliography titles of publications are replaced by corresponding symbols in this list. American A-1. Transactions of the American Institute of Mining Engineers, New York. A-2. Journal of the New York Microscopical Society, New York. A-3. Journal of the Franklin Institute, Philadelphia, Pa. A-4. The Metallographist, Boston, Mass. A-5. The Electrochemical and Metallurgical Industry, New York. A-6. Bulletin of the American Institute of Mining Engineers, New York. A-7. The Iron Trade Review, Cleveland, Ohio. A-8. The Journal of Physical Chemistry, Ithaca, N. Y. A-9. The Physical Review, New York. A-10. Van Nostrand&apos;s Electric Engineering Magazine, New York. English E-1. Proceedings of the Institution of Mechanical Engineers, London. E-2. Journal of the Iron and Steel Institute, London. E3. Proceedings of the Institution of Civil Engineers, London. E-4. Journal of the Chemical Society of London, London. E-5. Philosophical Magazine, London. E-6. Proceedings of the Royal Society of Edinburgh, Edinburgh., E7. Carnegie Scholarship Memoirs, London. E-8. Proceedings of the Royal Society of London, London. E-9. Chemical News, London. E-10. Philosophical Transactions of the Royal Society of London,, London. E-11. Transactions of the North-East Coast Institution of Engineers and Shipbuilders, Newcastle-on-Tyne E-12. Iron, London. E-13. Nature, London. E14. English Mechanic and World of Science, London.

Jan 6, 1914

THE iron and steel industry spent $1,170,000,000 in 1952 for improvements and expansion, with an accompanying rise of 9 million net tons in capacity to 117.5 million tons of ingots and steel for castings. More than $4,600,000,000 has been invested in the seven years following World War 11. An average of $1260 has been laid out every minute during those seven years for an increase in capacity of 25.6 million tons.

Jan 3, 1953

Organization Place Date 1919 Automotive Engineers New York, N. Y. Feb. 4-6 American Institute of Mining Engineers New York, N. Y. Feb. 17-20 New England Association of Gas Engineers Boston, Mass. Feb. 19 American Institute of Electrical Engineers New York, N. Y. Feb. 19-21 National Society for the Study of Education Chicago, Ill. Feb. 25-28 American Railway Engineering Association Chicago, Ill. Mch. 18-20 American Electrochemical Society New York, N. Y. Apr. 3-5.

Jan 2, 1919

By F. L. Robertson, C. H. Bacon, J. W. Till

A description is given of the development of a process for making low sulphur steel on furnaces fired with 2 1/2 pet sulphur oil. Slag and metal are analyzed at melt. Slag weight is estimated. A simple method for calculating necessary lime additions for making 0.025 and 0.035 pct sulphur steel is given. DURING the last 15 years John Summers & Sons have been confronted increasingly by the problem of producing a low sulphur steel from high sulphur materials. The principles adopted, the processes used, the data collected on a furnace specially set aside to study this problem, and speculation on future developments are dealt with in this paper. This study is limited to two melting shops which make sheet steel only, of the following analysis: C, 0.06 pct; Mn, 0.33; S, 0.04, 0.035, 0.03, and 0.025; and P, 0.02 and 0.015. All the processes described have reference to the manufacturing of this steel and are not necessarily applicable, without modification, to other steels. The raw materials used are given in Table I. Development of Process About 1934, Schenck&apos;s work on phosphorus was applied to frame quantitative rules for the removal of phosphorus, with great success. We could however, neither in our own work nor in the voluminous literature, find any assistance to frame quantitative furnace rules to remove sulphur. Perhaps, we should have persevered with Schenck&apos;s outstanding chapter on sulphur in The Physical Chemistry of Steelmaking, but we missed the importance of one (Ss) sentence on p. 478. "Evidently this ratio -------- is [S] the important quantity to be considered from the point of view of chemical reaction; it is clear that the sulphur content of the steel alone, as frequently given in the literature cannot suffice for judging the success of the reaction unless special details are given regarding the sulphur charge and the amount of slag."&apos; We were not however very successful in getting values for Schenck&apos;s "n" that agreed with (S) arrived at by our direct analysis. [S] In addition to Schenck&apos;s work much attention was given to V value. The formula selected for V was: (SCaO) — 1.57 (2 P2O5) (S SiO2) After plotting many charges a curve was obtained, based upon the relationship between the percentage sulphur in the finished steel and V value, Fig. 1. For a long time this was used as standard with about a 60 to 70 pct success on producer-gas fired furnaces, if all uprising scrap was used and no bought scrap used. An inspection of this curve shows clearly that it is not a quantitative manufacturing process, and that it was not sure enough to go to the trouble and expense of doing stage analysis for P,O,,

Jan 1, 1952