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By Frederick N. Rhines

BECAUSE of the nature of the environments in which metals are handled, it is natural that gases should be suspected of intruding into metallurgical operations, there to produce effects both beneficial and detrimental. The problem of tracing and controlling such effects is often made difficult by the complexity of the conditions surrounding 'their occurrence, even though the fundamental mechanisms involved may be simple and of familiar type. Many gas-metal reactions are known to be implemented by processes of diffusion. These form a homogeneous group of phenomena which become more readily understandable when viewed together, in that the knowledge gained from one serves to interpret the next. It is the purpose of the present paper to present, by means of examples drawn from practice, a brief survey, of the ways in which gas-metal diffusion serves and obstructs the purposes of the metal-fabricating industries. The selection of the cases described was made by consulting more than thirty-six practicing experts whose combined experience provided an extensive coverage of the field and who were in a position to supply examples of occurrences of present day interest. The response was generous and it is regrettable that space permits the description of only a limited number of typical examples with but brief mention of parallel cases. THE NATURE OF GAS-METAL DIFFUSION The term "gas-metal diffusion," although commonly used, is ambiguous in so far as it implies that a definite group of substances may be identified as gases and may be expected to behave in a manner distinct from other substances in association with metals. "Gases" such as oxygen and hydrogen when diffusing through a liquid or solid metal are properly components of the liquid or solid solution; they behave as alloying elements and are not to be distinguished in their diffusion characteristics from other elements, except that each has an individual rate of diffusion. On the other hand, a number of metals in certain temperature ranges are volatile to the extent that they may appear in the form of vapor in metallurgical operations. For the sake of greater definiteness, therefore, it will be convenient to- regard as "gas-metal diffusion" any process in which the result depends upon one or more of the diffusing elements appearing, at some stage, in the gaseous state, or as a compound gas. No element, gaseous or otherwise, can diffuse through a liquid or solid metal unless it is at least slightly soluble in that metal. The elements of low atomic number

Jan 1, 1944

By E. J. Pasierb, H. W. Paxton

Mavkers ill a diffusion couple in the iron-chromium system move towards the high chromium side indicating Dcr > DFe at the marker composition. By a combituztion of measurements of D& and D a: a function of composition, this is also shown independently. DFe is calculated as a function of composition. and shown to be in reasonable agreement with measured values by other workers. MEASUREMENTS of marker movements in diffusion couples have been used from time to time to demonstrate that a vacancy or interstitial mechanism may be operative. Since there is a possibility that ring diffusion1 may be operative in chromium, the present experiments are of interest in showing some non-ring mechanism in iron-chromium alloys around the equiatomic composition. EXPERIMENTAL PROCEDURE The movement of markers originally at the interface between 1-in. sq sections of pure Cr (6 mm thick) and outer slabs of 30 Cr-70 Fe alloy was followed as a function of time at temperatures from 1150" to 1425"C, in a Kanthal-wound furnace. Temperature control was +5°C over extended periods. The analyses of these alloys are given in Table I. Selection of suitable markers presented a considerable experimental problem; the eventual solution was to draw quartz rod down to 0.01 cm and seat this in V-grooves 0.01 cm deep on each side of the chromium prior to welding. A preliminary experiment in which the groove was machined in the alloy gave identical results. Welding was accomplished by passing a heavy current through specimens under moderate pressure in a helium atmosphere. This method produced good welds with a planar interface as shown by subsequent metallo-graphic investigation. Any markers which did not adequately fill their groove and showed subsequent contamination from the atmosphere during heat treatment were not considered reliable. The composite sample was ground and metal-lographically polished on the four sides perpendicular to the interface. Fiducial marks (deep milled slots) were made outside the diffusion zone to check on total volume change. All necessary measurements were made on a metallograph reading to +0.0005 cm. The samples were wrapped in tantalum foil and given diffusion anneals for times to 200 hr in carefully purified dry hydrogen in a sealed McDanel porcelain tube. Chromium-zirconium chips were introduced near the specimen as an additional getter. The specimens were cooled relatively slowly after the diffusion anneal to preserve the McDanel tube but no significant error in effective time at temperature was thereby introduced. At least 1 mm was ground off the surface before measurements were taken. It was observed that the grain size following short diffusion anneals was several mm and was appreciably larger in the 30 Cr alloy than in the pure Cr. No significant grain boundary penetration was present as indicated by the etch limit. The results are presented in the next section. Measurements of D were made by standard sectioning techniques with chemical analysis. Machining difficulties limited the

Jan 1, 1961

By C. Stansfield Hitchen

THE introduction of the logarithmic sector method of quantitative spectrography by Scheibe and Neuhäusser in 1928, and the subsequent .modification and improvement of the method by Twyman and Simeon, would seem to have marked yet a further advance in quantitative spec-trum analysis and its industrial application, inasmuch as it offers a simple means of eliminating some of the uncertainties inherent in the older methods based upon mere visual comparison of line intensities. In their recent admirable review of the position and capabilities of industrial spectroscopy, Brownsdon and van Someren1 say: Ways and means of facilitating the comparison of line-intensities so as to give them numerical values are helpful, and of these a logarithmic sector rotating in front of the slit appears to he one of the most promising; . . . the success recently experienced by the author in using this method for the examination of steels and solutions of metallic salts prompted him ,to investigate its possible use in estimating the impurities commonly present in crude and refined tin. The results of this investigation are submitted in the present paper. Details of a number of spectrographic analyses of tin for various impurities have already been published. Thus, Schweitzer2 describes the spectrographic examination of tin for lead, bismuth and cadmium, and was able to distinguish between such atomic percentages as 0.01, 0.05, 0.10, 0.30, 0.60, 1.20, 3.00 and 10.00. Negresco3 investigated the bismuth content of tin over a range of from 0.0005 to 35 per cent. Meggers, Kiess and Stimson4 compare spectrographic and chemical analyses of tin metal for copper, lead, iron, zinc, silver, nickel and bismuth. They stress also the value of spectrum analysis in the examination of tin used for boiler plugs, where the requirements that only minute quantities of impurities shall be present render the chemical analysis both tedious and difficult.

Jan 1, 1933

By P. S. Rudman

The solubility limit and the diffusivity of carbon in molybdenum have been obtained by duffising carbon into molybdenum rods from a Mo + Mo2C powder mixture. The solubility limit was taken as the long-time asymptotic limit of the rod composition. The diffusiv-ity was obtained from fractionally saturated rods from the rate of change of the average composition. Compositions were determined by chemical analysis. The solubility limit obtained is: WhILE the Mo-C system is important in refractory alloy technology neither the solubility limit nor the diffusivity of carbon in molybdenum is unambiguously known. In Fig. 1 the Mo-C phase diagram is presented. The heavy lines, the terminal solution solubility limit, and the eutectic temperature are results of the present investigation and will be discussed in detail later. However, it is readily seen that the previously published solubility limit determinations, Few and Manning1 and Fromm and ROy2 differ by up to an order of magnitude. The general form of Fig. 1, the Mo2C field, and a eu- tectic temperature -2200°C are due to an early Investigation by Sykes et a1.3 Although they did not determine the solubility limit, they did establish that the maximum at the eutectic temperature was about 1000 ppm. The only other prior data found on the solubility limit is from a lattice-parameter study by Speiser et a1 .,4 from which it can be concluded that the maximum solubility is greater than 1800 ppm. There does not appear to be any data oh the diffusivity of carbon in molybdenum. However, Samsonov and Epik5 have determined, from the rate of growth of an MozC layer, the diffusivity of carbon in Mo2C, and this has been erroneously interpreted, for example by ~c~eil,' as applicable to diffusion of carbon in molybdenum.

Jan 1, 1968

By M. J. McPherson

Having worked on the thermodynamics of air/liquid-water mixtures passing through the surface fans of deep mines, I find this paper of great interest and congratulate the authors on producing it. There are two matters, however, deserving discussion. First, the authors have described the classical theory of fog formation with fogging occurring at "supersaturation." In fact, the process of fog formation begins well below 100% humidity. The more strongly hygroscopic nuclei in the atmosphere will attract water molecules and begin to grow at a relative humidity perhaps as low as 70%. The process is a dynamic one with both condensation and evaporation taking place throughout the mixture on microscopic liquid surfaces. As saturation is approached, the rate of condensation accelerates rapidly producing the familiar reduction in visibility. Hygroscopic nuclei are present in all natural atmospheres and under the appropriate conditions of pressure and temperature, will produce clean fogs. However, if the air is polluted by particulates from combustion or other processes then the resultant coagulation with growing liquid particles may produce dense (and sometimes photochemical) smogs. It is this process that is likely to occur in underground mines when moist air is cooled below dew point. Second, the authors have summarized very well the individual measures that might alleviate the problem. In particular, I agree that neither heating nor refrigerating the air, by themselves, provides a satisfactory solution. However, there is a combination of these that provides a neat and effective control of fog formation. This involves a small, self-contained refrigeration unit within a duct but without the usual external heat rejection facility. The air is cooled below dew point and, hence, dehumidified on passing over the cold evaporator coils. The heat from the condenser is rejected back into the air down-stream from the water eliminator, as shown in [Fig. 1]. The duct configuration can be designed to create good mixing at the outlet.

Jan 1, 1984

By Will H. Coghill

In this investigation, the low-grade red iron ores of Alabama were examined by the use of "heavy solutions."' Ores are generally ground preparatory to concentration and as long as the concentrators make suitable products the effectiveness of the grinding is likely to be unquestioned; but when suitable products are difficult to make, an investigation becomes imperative. In such a case a dissection of the ore might be made to find the cause of the trouble. Such a condition of unsuitable products exists in the low-grade red iron ores of Alabama. They are difficult to concentrate. To be sure it might be said that the concentration of iron ores is a new thing and that the ore-dressing methods are undeveloped, but a glance at the industry reveals an abundance of methods and devices for almost all imlaginable conditions. Concentrating machinery has not been tested in this investigation. When the properties of the ores have been gleaned, the machinery may be used more effectively. Alabama Low-grade Red Iron Ores The Bureau of Mines has undertaken by laboratory methods to select the best means of concentrating the low-grade iron ores of Alabama. These ores constitute the parts of the ore bed left by selective mining. If more of the ore bed could be included in the current output, the mining cost would be reduced and longer life of the district would be insured. This advantage would be reflected by added permanence of churches, homes, schools and every undertaking in the commonwealth. The red ores chosen for this study of effectiveness of grinding are too low in lime to meet the requirements of the blast furnace. If lime is

Jan 1, 1927

By W. D. Robertson, D. A. Koss, A. J. Goldman

THE significance of the hcp (E) structure, which appears when Fe-Cr-Ni alloys (stainless steels) are transformed martensitically, has been the subject of considerable study and speculation.'-7 It has been proposed that the hcp structure is an intermediate phase in the transformation: fcc (austenite) — hcp (E) -bcc (0, martensite). However, recent studies by transmission electron microscopy6,7 have indicated that the hcp structure may be a consequence of the large shear strain (10 deg) associated with the fcc to bcc transformation. That is, the transformation to a bcc structure is accompanied by extensive dissociation of dislocations in the parent austenite, which has a low stacking-fault energy.'-'' X-ray diffraction analysis of the transformed alloy reveals a pattern of lines corresponding to an hcp structure, together with the parent austenite and the bcc product. The fact that the hcp structure is observed only in association with the bcc product in these alloys1'4'6'7 lends support to the conclusion that the hcp structure is a secondary product of the transformation. But, the evidence is circumstantial and more definite resolution of the two possibilities mains to be obtained. If the hcp structure is an intermediate product of the transformation, as in 1) above, then two distinct Ms temperatures should be observed, Ms and To evaluate this possibility, three different techniques that are particularly sensitive to the structural changes accompanying such transformations have been used in an attempt to detect two transformation temperatures in an Fe-15.1 Cr-11.7 Ni alloy: 1) high-sensitivity differential thermal analysis, 2) the temperature dependence of resonant frequency (elastic moduli), and 3) internal friction of cylindrical specimens vibrating in either longitudinal or torsional modes. To obtain the necessary sensitivity, a differential thermal analysis technique was developed for the purpose, Fig. 1. The differential temperature between a nickel standard and the specimen was amplified to produce a sensitivity of 0.02OC (0.7 v) in temperature difference. The specimen and the standard were surrounded by a copper block and the entire assembly was immersed in a solution of methyl and ethyl alcohol, freezing point, - 140OC, which provided the necessary thermal stability to reduce temperature fluctuations to negligible proportions. A cooling rate of about 1.5OC per min was obtained by bubbling liquid nitrogen through the liquid bath. In order to calibrate the experiment with respect to the evolution of heat in the transformation from fcc to hcp structures, differential cooling curves were obtained for an Fe-19.8 Mn alloy, which transforms martensitically to E.'"-' a Ms(e) temperature of 145°C was clearly defined by a temperature

Jan 1, 1964

By R. S. Archer

In the microscopic examination of aircraft-engine parts made of heat-treated alloy steels, the writer has been forcibly impressed by the failure of the usual etching processes to disclose any but gross defects in heat treatment. It seemed particularly desirable to bring out the grain size of the steel, which is indicated in the ordinary etching processes chiefly by the change in orientation of structure from grain to grain. After various attempts, a fairly successful method has been found, which is here presented in the hope that it may be of use to those who have occasion to examine these steels in the hcat-treated condition. The specimens worked with have been mostly chrome-nickel steels heat treated (that is, hardened and tempered) to a Brinell hardness of around 300. A few experiments with other specimens will be referred to later. Briefly, the method employed consists in etching the steel about 10 min. in a fresh solution of picric acid in ethyl alcohol, and then rubbing off the smudge of carbonaceous matter on moist broadcloth. Different samples of almost identical analysis, heat treatment, and physical properties (including resistance to impact) respond quite differently to this treatment. In some, the grain boundaries are developed quite readily, while in others, especially in those whose grain is unusually fine or in which the final hardening heat has not quite obliterated the previous crystallization, the results are more obscure. The exact time of etching to secure the best results also differs for various samples, and the greatest success is usually attained by a process of "tinkering." Such a process is illustrated in a series of micrographs, the first six of which were taken at a magnification of 300 diameters. The properties of the steel are as follows: Carbon, per cent............... 0.42 Brinell hardness.............. 293 Nickel, per cent................ 1.35 Yield point, pounds per square Chromium, per cent............. 0.90 inch........................ 131,000 Copper, per cent................ 0.025 Maximum strength, pounds per Manganese, per cent............ 0.74 square inch................. 144,500 Phosphorus, per cent............ 0.024 Elongation in 1 in., per cent... 28 Sulfur, per cent................ 0.036 Lod impact, foot-pounds...... 51 Reduction of area, per cent...... 57.3

Jan 1, 1920

By William S. Hannan, H. Rush Spedden

Flotation may be defined as a process whereby mineral particles are concentrated by selective adhesion to air-liquid interfaces. The process involves attachment of desired mineral particles to air bubbles, and removal of the mineralized air bubbles from the surface of the pulp as a mineral concentrate. Problem Although great strides have been made in understanding the principles of flotation, one part of the process which has not been adequately explained is the mechanism by which selected mineral particles become attached to air bubbles. A glance at the froth of an operating flotation cell demonstrates adequately that use of proper reagents and conditions mill result in such attachments; but how such attachment takes place is not definitely known. A better knowledge of this factor might lead to improved flotation practice either through altered machine design or the application of scientific innovations. Direct observation of the behavior of mineral particles and bubbles in an operating cell does not appear promising because of the complexity of the system. For this reason, conclusions concerning the problem must be deduced from theoretical considerations or from observation of simplified systems designed to reproduce conditions thought to exist in an operating cell. Present Theories Two mechanisms have been recognized as fundamental in particle-bubble attachment: gas precipitation and direct encounter. It is a simple matter to demonstrate in the laboratory that attachment can be brought about by either mechanism. As to the relative importance of the two in a particular flotation system, however, there is a divergence of views. Taggart1 states, Under exceptional circumstances sufficient force and time to effect attachment may conjoin in an ore pulp undergoing agitation, and a preformed bubble adhere to a collector-coated mineral particle, but the occurrence is rare. . . . Pulp-body froth flotation effects selection in the body of a conditioned pulp by causing gas bubbles to precipitate from solution in the liquid phase preferentially at the surfaces of collector-coated particles, and to cling to these particles, Gaudin2 states that, within the pulp body of an agitation machine, attachment of mineral particles to air bubbles occurs as a consequence of contact between the two. This theory has been supported by theoretical reasoning and much circumstantial evidence. Perhaps the most interesting bit of evidence in favor Of this theory js the difficulty in the flotation of fines. If attach-

Jan 1, 1949

By R. V. Riley

IN the metallographic examination of the alloys of iron and silicon, several investigators1-' have reported on the occurrence of an unusual type of etched structure, particularly in the alloys of higher silicon content. This, the so-called "barley shell" structure, has been observed with iron-silicon alloys over a wide range of silicon content, and under certain circumstances it can be seen upon the micro-sections of pure iron. The barley shell structure may be demonstrated most easily with iron-silicon alloys in the range 8 to 20 pct Si after etching in a hydrofluoric acid base etchant. Two etchants which produce the structure are: Corson's reagent, which is 2 parts hydrofluoric acid, 1 part nitric acid, and 2 parts glycerol; and picric acid reagent, which is 1 part hydrofluoric acid and 1 part saturated solution of picric acid in alcohol. Both when freshly prepared and used for etching commercial silicon-iron alloys containing 14 to 16 pct Si, invariably produce the barley shell structure shown in Fig. la. It is now well known that the barley shell structure is a pseudomorph and the true structure of an alloy of this composition consists of a single phase of silico-ferrite together with graphite as shown in Fig. lb. Lower silicon alloys and even pure electrolytic iron may also be etched in the above reagents to give the barley shell provided the etchant has been either: 1—Stored in contact with glass or silica, or 2—used previously for etching an iron containing silicon. Pure iron etched in perfectly pure hydrofluoric acid base etchants free from silicon contamination gives a normal structure free from the barley shells. Therefore, although the hydrofluoric acid in the reagent primarily is responsible for the barley shells, silicon, or its compounds, also must be present, either in the etching reagent or in the specimen. It was of considerable interest to the author to read the paper by Wachtell,? in which the barley shell etch was deliberately used for the identification of the boundaries of high and low silicon areas in diffusion experiments made upon laminate bars of compacted and sintered pure iron and ferrosili-con powders. This method of utilizing the barley shell etch is novel and in the hands of the investigator gave a useful differentiation between the high and low silicon areas in those specimens. For the reasons already given, however, the technique is not to be regarded as of universal application. Misleading results might be obtained, for example, if two or more specimens were etched in the same etchant. Fresh pure reagents only must be used each time. Provided this is done and the investigators are well aware of the limitations of the method, then the barley shell pseudomorph can be made of limited use in distinguishing between higher and lower silicon areas in a microspecimen of a ferrous material. The greatest of care must be exercised in the interpretation of the results which may be regarded as qualitative only and may, in fact, not be specific to silicon alloys.

Jan 1, 1952

By G. L. Oldright, T. B. Brighton, C. M. Dice

The base bullion from the lead blast furnace contains varying amounts of the impurities left in the smelter feed by the concentrator, regardless of the method of smelter operation. These impurities may be held in part in mechanical suspension rather than being present as true alloys. However, usually there is little free space in the crucible in which to separate these drosses before the bullion is taken from the lead well. When such a dross is melted in a laboratory crucible and allowed to cool, the products obtained are lead bullion, speiss, and matte in well separated layers. Typical analyses of layers are: Analyses. Per Cent Element Bullion Speiss Matte Pb.............................................. 92.0 41.2 38.3 Cu.............................................. 2.4 36.3 40.6 As............................................... 4.0 16.5 4.3 Sb............................................... 0.7 0.2 0.4 S................................................ 0.6 1.9 13.1 Fe............................................... 0.0 0.0 0.0 Totals......................................... 99.7 96.1 96.7 The absence of iron in these products drossed from the blast-furnace bullion proves that the impurities for the greater part are not simply finely divided blast-furnace speiss or matte that has been dissolved or dispersed in the lead, but are held in solution by the liquid metal and rise to its surface as infusible compounds when the temperature of the bath is lowered. In general, the drosses made locally are metal sulphides and arsenides and not oxidized compounds. The large content of metallic lead also does not seem to be retained because of oxidized compounds

Jan 1, 1937

By William A. Johnson, Robert F. Mehl

It is now recognized that several important types of reactions in metallic systems proceed by the formation of nuclei and the growth of these nuclei. The process of freezing is a simple example of this, as Tammann pointed out years ago.1 Tammann held that the rate of freezing is determined by a rate of nucleation, expressed as the number of nuclei formed per unit volume of unfrozen liquid per second, and a rate of growth of these nuclei, expressed as the linear rate of radial growth in units of length per second. For isothermal freezing the conception is simple; for ordinary freezing, extending over a range of temperature, it is not as simple, for the values of the two constants must change with change in temperature. There is ample evidence that the postulated mechanism is correct even though a quantitative derivation of the rate of isothermal or of ordinary freezing in terms of the two constants has been lacking. In recent years other reactions have been found to proceed in a similar fashion. It has been well established, particularly by Bain12-8 that the formation of pearlite from the eutectoid decomposition of the solid solution austenite proceeds in such a way, and Polanyi and Schmid, Tammann and Crone, Karnop and Sachs, and others9-11 have shown that the process of recrystallization proceeds in a similar way. Isothermal reaction rates have been determined for eutectoid decomposition by a number of investigators. Bain's2-8 work on the formation of pearlite from austenite is especially valuable in this respect—the type of isothermal reaction curve obtained, as illustrated in Fig. 13, showed an initial slow rate, accelerating to an intermediate maximum rate which then decelerated to the completion of the reaction; similar curves have been obtained by Wever and his collaborators.12 Other eutectoid decompositions show similar behavior: for example, the decomposition of the beta eutectoid in the copper-aluminum system, studied by Smith

Jan 1, 1939

By William A. Johnson, Robert F. Mehl

It is now recognized that several important types of reactions in metallic systems proceed by the formation of nuclei and the growth of these nuclei. The process of freezing is a simple example of this, as Tammann pointed out years ago.1 Tammann held that the rate of freezing is determined by a rate of nucleation, expressed as the number of nuclei formed per unit volume of unfrozen liquid per second, and a rate of growth of these nuclei, expressed as the linear rate of radial growth in units of length per second. For isothermal freezing the conception is simple; for ordinary freezing, extending over a range of temperature, it is not as simple, for the values of the two constants must change with change in temperature. There is ample evidence that the postulated mechanism is correct even though a quantitative derivation of the rate of isothermal or of ordinary freezing in terms of the two constants has been lacking. In recent years other reactions have been found to proceed in a similar fashion. It has been well established, particularly by Bain12-8 that the formation of pearlite from the eutectoid decomposition of the solid solution austenite proceeds in such a way, and Polanyi and Schmid, Tammann and Crone, Karnop and Sachs, and others9-11 have shown that the process of recrystallization proceeds in a similar way. Isothermal reaction rates have been determined for eutectoid decomposition by a number of investigators. Bain's2-8 work on the formation of pearlite from austenite is especially valuable in this respect—the type of isothermal reaction curve obtained, as illustrated in Fig. 13, showed an initial slow rate, accelerating to an intermediate maximum rate which then decelerated to the completion of the reaction; similar curves have been obtained by Wever and his collaborators.12 Other eutectoid decompositions show similar behavior: for example, the decomposition of the beta eutectoid in the copper-aluminum system, studied by Smith

Jan 1, 1939

By J. W. Stewart

THE aim of this paper is to point out the various ways in which design is taught in standard four-year mining engineering curricula in American colleges and universities; to discuss the reasons apparently justifying the great diversity of procedure that exists along this line; and to indicate possible solutions to the difficulties now attending the teaching of design. A study was made of typical four-year mining engineering curricula in 15 colleges and universities of the United States (Table I). Great diversity in content of the various design courses, if taught as described, became apparent immediately. It appeared that it might be both interesting and instructive if the cause for this colorful variety could be found. Was the cause local mining conditions, departmental individuality, or actual necessity? Study of the school catalogues revealed that the various design courses could be classified into two fairly distinct types; namely, (I) those dealing with mine equipment or structures, and (2) those dealing with underground layout of mine workings. It seemed reasonable to label the first type of course "mining design" and the second type "mine design." Some such distinction must have been in the minds of mining educators, for we find both names (i.e., mine design and mining design) used to designate the design courses included in the various mining curricula. Unhappily, the name and the apparent content of such courses do not, in all instances, conform to the classification made here, although in most instances such conformation does obtain (Table I), It is possible that in the exceptional case the method of teaching a design course, and consequently the content of it, may have been changed at some time without change in the name of the course. Apparently only 3 of the I5 schools made an effort to cover both types of design in their curricula (Table I). Two other schools did not list or describe any course of study that could with certainty be taken as a design course. Of the remaining 10 schools, 9 gave a mining-design type of course and one gave a strictly mine-design type. Obviously, the preponderance of design courses afforded are of the mining-design type. Why? To answer this question, it is necessary to make a study of the prerequisites for the two types of design courses taught. In all schools the design courses were taught in the senior year; in eight, design was taught throughout both semesters; in two, it was taught during the first semester only; and in three it was taught during the second semester only. Consequently, excepting the last three cases noted, it is obvious that all prerequisites for a design course should be completed by the end of the junior year. PREREQUISITES What are the probable prerequisites for the different kinds of design courses as they appear to be taught? Let us take first the case of the mine-design type of course, having to do with layout of underground workings. Here it would seem that logical

Jan 1, 1941

By D. G. Westlake, D. T. Peterson

The saturation solubility of thorium dihydride in thorium was studied by saturation of samples and subsequent analysis. The solubility increased from about 1 at. pct at 300°C to above 20 at. pct at 800 °C. Over this temperature range the log of the solubility was a linear function of the reciprocal absolute temperature for thorium of good purity. The heat of solution of thorium dihydride was found to be 7.9 kcal per atom of hydrogen in crystal bar thorium and 6.6 kcal per atom of hydrogen in Ames thorium, The important effect of hydrogen on the physical and mechanical properties of many metals is receiving increasing recognition. The basic physical and chemical data necessary to help explain the observed effects of hydrogen on the mechanical proper ties of metals are all too often not available. The solubility of hydrogen in thorium metal was determined to provide a portion of this basic data for the thorium-hydrogen system. The absorption of hydrogen by thorium metal and the formation of thorium hydrides was studied by several investigators, beginning in 1891, and their work is summarized in Gmelin's Handbuch.1 No effort was made to determine the extent of solid solubility in the metal in these early investigations and the impure metal available made interpretation of the results uncertain. Nottorf2 reported the results of a careful study of pressure-composition isotherms for the thorium-hydrogen system. The principal interest in this work was in the composition and dissociation pressures of the thorium hydrides. Mallett and campbel13 reported the pressure-composition isotherms for the thorium-hydrogen system up to the composition of thorium dihydride. The saturation solubility of thorium dihydride in thorium was reported to be 13 at. pct at 650°C and 23 at. pct at about 900° C. Mallett and Campbell used thorium metal which had been prepared by the calcium reduction of thorium tetra-fluoride or thorium oxide. The results obtained with thorium of these two types agreed within the experimental error. PROCEDURE AND MATERIALS Procedure—The method used to determine the solubility was to saturate a sample of thorium with hydrogen and analyze a portion of the saturated sample. This method was chosen rather than a determination of pressure-composition isotherms since it was much less time consuming and could be applied at temperatures at which the equilibrium hydrogen pressure was too low to measure. The

Jan 1, 1960

By D. H. Polonis, J. G. Parr

IN a recent paper on titanium-rich Ti-Fe alloys,' the hardness of quenched powder specimens was given, together with the amounts of martensitic a they contained. The values disagreed in two respects with previous determinations that Worner² made on lump specimens: 1—Some martensitic a' is formed in powder specimens of alloys containing up to 12 atomic pct Fe. On the other hand, Worner reports that, although his results on quenched lumps are not conclusive, alloys containing more than about 4 pct Fe "appear to consist of retained ß'' although they "may not be strictly unaltered solid solutions." 2—According to Worner, quenched lump specimens show a maximum hardness at a composition about 3.5 pct Fe. Earlier -experiments by the authors showed a maximum hardness of martensitic alloys in powder form at 10 pct Fe. Accordingly, more experiments have been conducted in order to confirm these differences and to determine with more accuracy the minimum composition of quenched lump specimens that consist entirely of retained ß. Lump samples?x?x1/20 in. were quenched from 1000°C in helium and, on the whole, showed similar hardness values to the specimens that Worner water-quenched from 950°C. The hardness curve the authors obtained shows a more pronounced peak, but in other respects it is very similar to Worner's curve (Fig. 1). While it was possible to make fairly reliable measurements of the percentage of martensitic a in quenched powders (by Geiger spectrometer), the solid samples allowed only approximate estimates to be made from visual observation of line intensities on film. Retained ? begins to appear in quenched lumps containing 0.2 pct Fe; at 2.2 pct Fe there are approximately equal quantities of ß and a'; in a 4.7 pct Fe alloy only a trace of a' appears. These results are represented as a curve on Fig. 1. The hardness and constitution of powder samples were verified by repeating both types of quenching experiment described in the earlier paper.' Identical results were obtained by the two methods, and they agreed with the figures published previously (Fig. 1). The appearance of the martensitic structure under the microscope is shown in Figs. 2 and 3. The mar-tensite needles are coarser in the lump; otherwise the structures are similar. Three conclusions are made at this juncture: 1— The properties of quenched lumps reported by Worner are confirmed, on the whole. The differences between them and the properties of powders are probably due to an effect of specimen size. Differences of behavior in various sizes of specimen have been observed previously in martensite reactions in Fe-Mn alloys3 and in Cu-A1 alloys. 2—The maximum hardness of both quenched lumps and quenched powders appears at a composition where martensite formation has all but ceased. In this respect, powders and lumps behave similarly. 3—Martensitic a' has essentially the same microscopic appearance both in powders and lumps. Acknowledgment This work is part of a program sponsored by the Defegce Research Board of Canada, Project No. 425.

Jan 1, 1956

By J. J. Mulligan

Introduction Coal is found in every major geographic region through-out Alaska and in two offshore areas. Since about 1852, more than 100 small mines have opened and closed. In 1981 and 1982 production was almost entirely from one mine in central Alaska. Clearly, the utilization of Alaska's abundant coal resources presents political, economic, and technical problems that are far from solution. Location and Physical Features Figure 1 illustrates the geographical and geological similarity between Alaska and the western US. Alaska's Arctic region generally resembles Wyoming and the Dakotas. The Brooks Range is an extension of the Rocky Mountains. The central region of Alaska between the Brooks Range and the Alaska Range bears a general resemblance to the basin and range country of the western US. The southcentral and southeastern regions have a similar resemblance to the Sierra Nevadas and the West Coast. The Arctic, the central, and the southcentral regions have major coal fields. The southeast region has scattered occurrences. The topographic, climatic, and economic characteristics of each are different. These differences have a large effect on practical mining methods. Description of Alaskan Coal Coal deposits known in Alaska are almost all of Cretaceous or Tertiary age, much younger than the Carboniferous coal deposits of eastern and midwestern states. Consequently, most Alaskan coals have a higher moisture content and a lower heat value. Most Alaskan coals also have a much lower sulfur content. Low volatile bituminous, and anthracite coals occur in Alaska, but most Alaskan coals range downward in rank from high volatile bituminous to subbituminous and lignite. Alaskan coals are similar to coals of the northern Great Plains and the Rocky Mountains. Arctic Region Northern Alaska Coal Fields Northern Alaska coal fields are by far the largest group of coal deposits in Alaska (Fig. 2). Coal-bearing rocks extend from the foothills of the Brooks Range about 160 km (100 miles) northward to within about 80 km (50 miles) of the Arctic coast. The principal known occurrences are between the Colville River and the western coast. However, coal has been found eastward almost to the Canning River and westward under the Arctic Ocean. The northern Alaska coal fields are in a series of Cretaceous rocks that suggest a deltaic depositional environment. The beds tend to occur in series of up to eight or nine beds totaling 6-9 m (20-30 ft) of coal. However, beds 6-12 m (20-40 ft) thick have been reported, and beds 1-3 m (3-10 ft) thick seem to be relatively common. Including thin seams, coal in some places makes up about 10% of the stratigraphic section. However, no area has been explored in sufficient detail to block out any large body of reserves or to make reliable estimates of the total resource. Observation points in drill holes and along river and stream banks are few and far between. Coals in northern Alaskan fields tend to range in rank from bituminous, where moderately folded and faulted in the foothills, to subbittuminous in the gently folded rocks under the coastal plain. Coals toward the eastern extremities of the coal fields may be of Tertiary age and lower in rank, but the same general correlation between degree of folding and increase in rank can be expected. Some higher rank coals in the foothills belt are known to have coking properties but most, and possibly all, require

Jan 1, 1984

By R. P. Smith

Iron-carbon alloys containing a single-phase austenite region and a two-phase azcstenite + cementite region at the desired temperature were prepared by partial carburization of iron or partial decarburization of carburized iron. Each sample was held at a fixed temperature until equilibrium was achieved. Analysis of the austenite for carbon then gave the solubility of cementite in austenite. Solubility measzcrements were made for the temperature range 734° to 1012°C. These values together with other data give 7560 cal for the mean heat of solution of cementite in austenite, and 0.765 pct C for the eutectoid composition of austenite. They also indicate that graphite is the stable phase at all temperatures between the eutectoid and eutectic temperature. Measurements of the solubility of cementite in austenite at 927oand 1011 "C, using a method based on the equilibration of iron with boro-cementites, are reported. The solubility of cementite in austenite (?-iron) has been computed by Darken and Gurry1 from the observed solubility of graphite in austenite, and the thermodynamic properties of pure iron and of iron-carbon alloys. They have shown that the solubility of cementite is greater than that of graphite in the temperature range between the eutectoid and eutectic, and thus that cementite is metastable with respect to graphite and austenite saturated therewith. Since their computation is not in accord with the earlier experimental work of Mehl and wells,' the present direct determination of the solubility of cementite in austenite was undertaken. EXPERIMENTAL PROCEDURE Each iron rod about 1/2 in. O.D. by 4 in. was first carburized at a temperature and with a H2-CH4 gas mixture such that the carbon content would be greater than that corresponding to the solubility of cementite in austenite at the desired (lower) temperature; sufficient carburizing time was allowed that the carbon content became substantially uniform, as illustrated by Curve A, Fig. 1. The sample was then partially decarburized with a hydrogen-water vapor mixture, giving a carbon distribution as schematically illustrated by Curve B. The sample was then held in a helium atmosphere at the temperature at which the solubility was to be determined until the decarburized portion of the sample came to equilibrium with that containing cementite. Curve C of Fig. 1 represents schematically the final carbon distribution; the horizontal portion corresponds to the carbon content of austenite saturated with cementite. To bring the sample to room temperature without change in the carbon distribution and in machinable condition, it was first quenched in a salt pot at 480°C, then in water at room temperature. Successive layers were machined from the center 2 in. of the sample and analyzed for carbon by the usual

Jan 1, 1960

By Ö. Valla, A. Muan, K. Grjotheim

The solid miscibility gap between CaO and "FeO" in the system CaO-"FeO" in contact with metallic iron gradually closes as MnO is added as a third component. On the liquidus surface of the system CaO-"FeO"-MnO, this situation gives rise to a boundary curve which originates in the bounding system CaO-''FeO", proceeds a short distance into the composition triangle of the ternary system, and then vanishes. A new approach has been used to follow the course of this boundary curve. It is shown that the curve vanishes at a much lower temperature and at much lower MnO contents than has been inferred previously. The oxides CaO, "FeO", and MnO together with SiO2 are the major components of the slag phase formed in the basic oxygen process. Hence, the system CaO-"Fe0"-MnO is of considerable technological interest. In addition, the system is theoretically interesting. The three oxides above all have sodium chloride structure. The size differences among the cations are such that in the bounding "binary"* systems CaO-MnO and "FeO"-MnO complete solid-solution series are formed,1,2 whereas in the system CaO-"FeO" there is only limited mutual solubility in the solid state,3 see Fig. 1. Hence, a solid miscibility gap exists in a part of the "ternary"* system Ca0-"Fe0"-Mn0, and a liquidus boundary curve originates at the peritectic point, point a in the insert in Fig. 1, in the system CaO-"FeO", extends a certain distance into the ternary system, and then vanishes. Very little quantitative information on the system Ca0-"Fe0"-Mn0 is available in previous literature. Fischer and Feischer4 sketched isothermal sections at 1600° and 1700°C, and estimated that the vanishing boundary curve extends to approximately 1650°C and a composition of 42 wt pct MnO. The work to be described in the following was aimed at locating experimentally the "vanishing" liquidus boundary curve, determining its end point, and deriving representative isothermal sections below and above the temperature of the end point of this curve. EXPERIMENTAL METHODS The phase relations were determined by the well-known quenching method. (For a description of this method as applied to oxide systems, see the original paper of Shepherd, Rankin, and wright.5) Prereacted oxide mixtures of desired compositions were contained in iron crucibles and heated in a vertical tube furnace in an atmosphere of purified nitrogen. After equilibrium was judged to have been attained, the samples were quenched to room temperature, the phases present were identified by microscopic and X-ray examination, and total iron oxide contents were determined by chemical analysis. "Fisher Certified" reagents (MnCO3, CaCO3, Fe2O3, and Fe) served as starting materials. The calcium carbonate and ferric oxide were heated in air at 400° and 800°C, respectively, for 24 hr prior to use. Manganese oxide was prepared by decomposing the carbonate in a graphite crucible in hydrogen atmosphere at 1000°C. The product was ground under acetone to -100 mesh. The iron powder was used directly without any preparation. Dicalcium ferrite was used as a starting material for some mixtures. It was made by mixing some of the above prepared CaCO3 and Fe2O3 in proportions corresponding to the formula 2CaO. Fe2O3. This mixture was then fired in air for

Jan 1, 1969

By Horace F. Silliman, Curtis L. Wilson, Eugene C. Little

The change in electrical resistance and Rockwell hardness (16-100-B) of copper alloys containing Ni2Si and Co2Si was determined by annealing the quenched solid solutions at various temperatures for various lengths of time. The rate of precipitation of Nisi, as measured by the rate of decrease of electrical resistance and increase of hardness, increased with annealing temperature up to a certain point, depending on the percentage of Ni2Si present. At these temperatures discontinuities in the rate: change occurred. Similar discontinuities in the Co2Si alloys were no The solubility of Co2Si in copper was found to be 5 per cent at 970" DISCUSSION (Robert F. Mehl presiding) R. I?. Mehl, Pittsburgh, Pa. (written discussion).—The electrical conductivity and hardness curves reported in this paper are interesting, particularly because many of the anomalies of the precipitation processes are evident from such curves. The title of the paper, however, is deceptive, for it implies that measurements of electrical conductivity and hardness are suitable to determine the rate of precipitation. Neither of these methods is suitable for a quantitative measurement of rates of reaction or of precipitation in the solid state. Electrical conductivity in some alloys shows an anomalous increase during the first stages of aging at low temperatures; it is notably sensitive to strain and to state of subdivision. I have plotted the conductivity curve representing the decomposition of the phase at 555" C. in the copper-aluminum system, given in the paper by Smith and Lindlief (Fig. 47, p. 93) as a rate of reaction curve, and compared it with the curve determined by area evaluation (Fig. 7); these two curves are not coincident. Hardness is likewise very uncertain, for it is so much dependent upon particle size. Of the various methods proposed for the study of rates of reaction and precipitation, the evaluation of volume of reaction product from the respective area of matrix and reaction product on the photomicrograph is the most trustworthy; suffering, perhaps, only from low sensitivity during the early stages. This method, used originally by Davenport and Bain and now by Smith and Lindlief, is suitable for

Jan 1, 1933